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Sample records for cyanamides

  1. Prebiotic condensation reactions using cyanamide

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

    Condensation reactions in cyanamide, 4-amino-5-imidazole-carboxamide and cyanamide, imidazole systems under dehydrating conditions at moderate temperatures (60 to 100 deg C) were investigated. The cyanamide, imidazole system was used for synthesis of palmitoylglycerols from ammonium palmitate and glycerol. With the addition of deoxythymidine to the former system, P1, P2-dideoxythymidine 5 prime-phosphate was obtained; the same cyanamide, 4-amino-5-imidazole-carboxamide system was used to synthesize deoxythymidine oligonucleotides using deoxythymidine 5 prime-phosphate and deoxythymidine 5 prime-triphosphate, and peptides using glycine, phenylalanine or isoleucine with adenosine 5 prime-triphosphate. The pH requirements for these reactions make their prebiotic significance questionable; however, it is conceivable that they could occur in stable pockets of low interlayer acidity in a clay such as montmorillonite.

  2. Quantification of cyanamide contents in herbaceous plants.

    PubMed

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

    2006-09-01

    Cyanamide (NH2CN) is found in nature, although it has long been recognized as an industrial product. Distribution of cyanamide in the plant kingdom was investigated using a direct quantitative determination method to detect and measure cyanamide by stable isotope dilution gas chromatography-mass spectrometry (the SID-GC-MS method). The SID-GC-MS method proved to be a robust way to quantify cyanamide contents in the extracts of 101 species of herbaceous plants. The average recovery of cyanamide from all plants tested was 55.6+/-20.3%. Vicia villosa and V. cracca contained cyanamide at 369-498 microg/gFW and 3,460-3,579 microg/gFW respectively, while the other 99 species contained no detectable cyanamide (<1 microg/gFW). This result suggests that distribution of cyanamide in the plant kingdom is limited and uneven. PMID:16960361

  3. 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. PMID:16644540

  4. 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

  5. Cyanamide is biosynthesized from L-canavanine in plants.

    PubMed

    Kamo, Tsunashi; Sakurai, Sakae; Yamanashi, Tatsuya; Todoroki, Yasushi

    2015-01-01

    Cyanamide had long been recognized as a synthetic compound but more recently has been found as a natural product from several leguminous plants. This compound's biosynthetic pathway, as yet unelaborated, has attracted attention because of its utility in many domains, such as agriculture, chemistry, and medicine. We noticed that the distribution of L-canavanine in the plant kingdom appeared to include that of cyanamide and that the guanidino group structure in L-canavanine contained the cyanamide skeleton. Here, quantification of these compounds in Vicia species suggested that cyanamide was biosynthesized from L-canavanine. Subsequent experiments involving L-[guanidineimino-(15)N2]canavanine addition to young Vicia villosa seedlings resulted in significant incorporation of (15)N-label into cyanamide, verifying its presumed biosynthetic pathway. PMID:26013398

  6. Cyanamide is biosynthesized from l-canavanine in plants

    PubMed Central

    Kamo, Tsunashi; Sakurai, Sakae; Yamanashi, Tatsuya; Todoroki, Yasushi

    2015-01-01

    Cyanamide had long been recognized as a synthetic compound but more recently has been found as a natural product from several leguminous plants. This compound’s biosynthetic pathway, as yet unelaborated, has attracted attention because of its utility in many domains, such as agriculture, chemistry, and medicine. We noticed that the distribution of L-canavanine in the plant kingdom appeared to include that of cyanamide and that the guanidino group structure in L-canavanine contained the cyanamide skeleton. Here, quantification of these compounds in Vicia species suggested that cyanamide was biosynthesized from L-canavanine. Subsequent experiments involving L-[guanidineimino-15N2]canavanine addition to young Vicia villosa seedlings resulted in significant incorporation of 15N-label into cyanamide, verifying its presumed biosynthetic pathway. PMID:26013398

  7. 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

  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 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

  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 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

  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. 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

  12. 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

  13. 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

  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. Direct quantitative determination of cyanamide by stable isotope dilution gas chromatography-mass spectrometry.

    PubMed

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

    2005-12-01

    Cyanamide is a multifunctional agrochemical used, for example, as a pesticide, herbicide, and fertilizer. Recent research has revealed that cyanamide is a natural product biosynthesized in a leguminous plant, hairy vetch (Vicia villosa). In the present study, gas chromatography-mass spectrometry (GC-MS) equipped with a capillary column for amines was used for direct quantitative determination of cyanamide. Quantitative signals for ((14)N(2))cyanamide, ((15)N(2))cyanamide (internal standard for stable isotope dilution method), and m-(trifluoromethyl)benzonitrile (internal standard for correcting errors in GC-MS analysis) were recorded as peak areas on mass chromatograms at m/z 42 (A(42)), 44 (A(44)), and 171 (A(IS)), respectively. Total cyanamide content, ((14)N(2))cyanamide plus ((15)N(2))cyanamide, was determined as a function of (A(42)+A(44))/A(IS). Contents of ((14)N(2))cyanamide and ((15)N(2))cyanamide were then calculated by multiplying the total cyanamide content by A(42)/(A(42)+A(44)) and A(44)/(A(42)+A(44)), respectively. The limit of detection for the total cyanamide content by the GC-MS analysis was around 1ng. The molar ratio of ((14)N(2))cyanamide to ((15)N(2))cyanamide in the injected sample was equal to the observed A(42)/A(44) value in the range from 0.1 to 5. It was, therefore, possible to use the stable isotope dilution method to quantify the natural cyanamide content in samples; i.e., the natural cyanamide content was derived by subtracting the A(42)/A(44) ratio of the internal standard from the A(42)/A(44) ratio of sample spiked with internal standard, and then multiplying the resulting difference by the amount of added ((15)N(2))cyanamide (SID-GC-MS method). This method successfully gave a reasonable value for the natural cyanamide content in hairy vetch, concurring with the value obtained by a conventional method in which cyanamide was derivatized to a photometrically active compound 4-cyanimido-1,2-naphthoquinone and analyzed with reversed

  16. Carbon sources of natural cyanamide in Vicia villosa subsp. varia.

    PubMed

    Kamo, Tsunashi; Kasahara, Ryohei; Abe, Shun; Hirota, Mitsuru; Sugano, Mami; Yamaya, Hiroko; Hiradate, Syuntaro; Fujii, Yoshiharu

    2010-10-01

    The ¹³C labels of [¹³C]carbon dioxide and D-[¹³C₆]glucose were incorporated into cyanamide (NH₂CN) when they were administered to Vicia villosa subsp. varia shoots. In contrast, the administration of sodium [2,3-¹³C₂]pyruvate did not affect the relative area of the [M + 1]+ ion of cyanamide in the gas chromatography-mass spectrometry analysis. [2,3-¹³C₂]pyruvate was incorporated into organic acids that are part of the citric acid cycle, such as succinate and fumarate, confirming that the shoots absorbed and metabolised it. These observations demonstrated that the carbon atom of cyanamide is derived from any of the carbohydrates that are present upstream of pyruvate in the metabolic pathway. PMID:20954091

  17. Effects of Hydrogen Cyanamide Application Rates and Timing on Fruit and Foliage of 'Climax' Rabbiteye Blueberry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A field study was conducted to evaluate the effects of flower bud pruning or utilizing differing rates of hydrogen cyanamide, on development of vegetative and floral buds, as well as on leaf area, vegetative coverage, fruit damage and development, and yield. In this study, hydrogen cyanamide applica...

  18. Silver(I)-Mediated Phosphorylation/Cyclization Cascade of N-Cyanamide Alkenes for Divergent Access to Quinazolinones and Dihydroisoquinolinones.

    PubMed

    Zheng, Jing; Zhang, Yan; Wang, Dahai; Cui, Sunliang

    2016-04-15

    A silver(I)-mediated phosphorylation/cyclization radical cascade of N-cyanamide alkenes has been developed. The addition of in situ generated phosphorus radical to N-cyanamide alkenes triggers the cascade, resulting in late-stage cyclization toward divergent access to 4-quinazolinones and dihydroisoquinolinones. Both terminal and internal N-cyanamide alkenes are applicable in this protocol, and the cyclizations are consistent with Baldwin's rule. PMID:27026261

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

    DOEpatents

    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.

  20. Quantification of cyanamide in young seedlings of Vicia species, Lens culinaris, and Robinia pseudo-acacia by gas chromatography-mass spectrometry.

    PubMed

    Kamo, Tsunashi; Takemura, Tomoko; Wasano, Naoya; Fujii, Yoshiharu; Hiradate, Syuntaro

    2012-01-01

    We quantified the cyanamide content of young leaves of nine Vicia species, Lens culinaris, and Robinia pseudo-acacia using a modified analytical procedure that made it possible to measure the cyanamide content of a single leaf. Recent molecular phylogenetic analysis suggests that cyanamide is present in V. benghalensis, which is placed in a monophyletic group with cyanamide-biosynthesizing plants, V. villosa and V. cracca; this suggestion was verified. PMID:22785492

  1. 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

  2. Seasonal Effects of a Late Application of Hydrogen Cyanamide on 'Climax' Rabbiteye Blueberry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A field study was conducted to evaluate the effects of hydrogen cyanamide (H2CN2) on flower and leaf buds, foliage, and fruit of 'Climax' rabbiteye blueberry (Vaccinium ashei, Reade), a cultivar exhibiting erratic spring foliation following mild winters. Stems of 'Climax' in several stages of flower...

  3. 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.

  4. 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. PMID:21573814

  5. Limited distribution of natural cyanamide in higher plants: occurrence in Vicia villosa subsp. varia, V. cracca, and Robinia pseudo-acacia.

    PubMed

    Kamo, Tsunashi; Endo, Mai; Sato, Masae; Kasahara, Ryohei; Yamaya, Hiroko; Hiradate, Syuntaro; Fujii, Yoshiharu; Hirai, Nobuhiro; Hirota, Mitsuru

    2008-03-01

    Cyanamide (NH2CN) has recently been proven to be a natural product, although it has been synthesized for over 100 years for agricultural and industrial purposes. The distribution of natural cyanamide appears to be limited, as indicated by our previous investigation of 101 weed species. In the present study, to investigate the distribution of natural cyanamide in Vicia species, we monitored the cyanamide contents in V. villosa subsp. varia, V. cracca, and V. amoena during their pre-flowering and flowering seasons. It was confirmed that V. cracca was superior to V. villosa subsp. varia in accumulating natural cyanamide, and that V. amoena was unable to biosynthesize this compound under laboratory condition examined. The localization of cyanamide in the leaves of V. villosa subsp. varia seedlings was also clarified. In a screening study to find cyanamide-biosynthesizing plants, only Robinia pseudo-acacia was found to contain cyanamide among 452 species of higher plants. We have investigated 553 species to date, but have so far found the ability to biosynthesize cyanamide in only three species, V. villosa subsp. varia, V. cracca and R. pseudo-acacia. PMID:18160082

  6. The effect of imidazole, cyanamide, and polyornithine on the condensation of nucleotides in aqueous systems.

    NASA Technical Reports Server (NTRS)

    Ibanez, J.; Kimball, A. P.; Oro, J.

    1971-01-01

    Development of two models for the condensation of nucleotides under possibly prebiotic conditions. In the first of these models this type of reaction is promoted by the presence of imidazole and substituted imidazole compounds. The second model involves the condensation of mononucleotides with cyanamide in the presence and absence of a prototemplate such as polyornithine. A tentative mechanism for the role of imidazole catalysis in phosphodiester bond formation between adjacent TMP molecules is suggested.

  7. Radical migration of substituents of aryl groups on quinazolinones derived from N-acyl cyanamides.

    PubMed

    Larraufie, Marie-Hélène; Courillon, Christine; Ollivier, Cyril; Lacôte, Emmanuel; Malacria, Max; Fensterbank, Louis

    2010-03-31

    A newly designed radical cascade involving N-acyl cyanamides is reported. It builds on aromatic homolytic substitutions as intermediate events and leads to complex heteroaromatic structures via an unprecedented radical migration of a substituent on aryl groups of quinazolinones (hydrogen or alkyl). Mechanistic considerations are detailed, which allowed us to devise fine control over the domino processes. The latter could be predictably stopped at several stages, depending on the reaction conditions. Finally, a surgical introduction of a trifluoromethyl substituent on a quinazolinone was achieved via the reported migration. PMID:20205425

  8. 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.

  9. 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

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

    PubMed

    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

  11. THE EFFECTS OF CHILL HOUR ACCUMULATION ON HYDROGEN CYANAMIDE EFFICACY IN RABBITEYE (VACCINIUM ASHEI READE) AND SOUTHERN HIGHBUSH BLUEBERRY CULTIVARS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A controlled environment study was conducted to evaluate the effects of chill-hour accumulation on the time of application and the resulting efficacy of the plant growth regulator, hydrogen cyanamide (H2CN2) in both rabbiteye and southern highbush blueberry cultivars. Application of H2CN2 at the in...

  12. 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.

  13. Fabrication of nanocomposites composed of silver cyanamide and titania for improved photocatalytic hydrogen generation.

    PubMed

    Meng, Hao; Li, Xiaoxue; Zhang, Xia; Liu, Yufeng; Xu, Yan; Han, Yide; Xu, Junli

    2015-12-14

    Highly efficient composite photocatalysts composed of silver cyanamide (Ag2NCN) and anatase titania (TiO2) were fabricated through a chemical precipitation process of silver nitrate and cyanamide in TiO2 suspensions. The TiO2 nanoparticles around 15 nm were immobilized on the surface of rectangular Ag2NCN particles to form a hetero-structure, and the contents of TiO2 were varied to tune the structure and the photocatalytic performances. In comparison with single TiO2 or Ag2NCN, the TiO2/Ag2NCN nanocomposites exhibited a prominent improved photocatalytic activity in the hydrogen generation, and the hydrogen evolution rate (1494.0 μmol (g h)(-1)) was higher than most of the reported TiO2-composite photocatalysts. Based on the structure investigation, the photocatalytic mechanism of these TiO2/Ag2NCN nanocomposites was proposed. The enhanced photocatalytic activity was attributed to three points: the matched energy level between TiO2 and Ag2NCN promoted the electron-hole transfer and thus inhibited the recombination of photogenerated electrons and holes; the great electron storage capacity of metallic silver produced in the photocatalytic process also facilitated the charge separation; in addition, the expanded absorption spectrum because of the composite structure enhanced the UV and visible light response ability. These TiO2/Ag2NCN nanocomposites also presented good photocatalytic stability in the typical cycle tests. This work provided new insights into fabricating highly efficient composite photocatalysts containing silver and TiO2 for hydrogen generation. PMID:26515664

  14. 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.

  15. Prebiotic-Like Condensations of Cyanamide and Glyoxal: Revisiting Intractable Biotars.

    PubMed

    Lavado, Nieves; Escamilla, Juan Carlos; Ávalos, Martín; Babiano, Reyes; Cintas, Pedro; Jiménez, José Luis; Palacios, Juan Carlos

    2016-09-12

    We report a detailed investigation into the nature of products that are generated by the reactions of cyanamide and glyoxal, two small molecules of astrochemical and prebiotic significance, under different experimental conditions. The experimental data suggest that the formation of oligomeric structures is related in part to the formation of insoluble tholins in the presence of oxygen-containing molecules. Although oligomerization proceeds well in water, product isolation turned out to be impractical. Instead, solid precipitates were obtained easily in acetone. Crude mixtures have been thoroughly scrutinized by spectroscopic methods, in particular NMR and mass spectroscopy (ESI mode), which are all consistent with the generation of a few functional groups that are embedded into regular chains of five- and six-membered rings, thereby pointing to a supramolecular organization. Three different models of cross-condensation and chain growth are suggested. These synthetic explorations provide further insights into the formation of complex organic matter in interstellar scenarios and extraterrestrial bodies that might have played a pivotal role in chemical evolution. PMID:27455123

  16. 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.

  17. Rotation and Rotation-Vibration Spectroscopy of the 0+-0- Inversion Doublet in Deuterated Cyanamide

    NASA Astrophysics Data System (ADS)

    Kisiel, Zbigniew; Kraśnicki, Adam; Jabs, Wolfgang; Herbst, Eric; Winnewisser, Brenda P.; Winnewisser, Manfred

    2013-10-01

    The pure rotation spectrum of deuterated cyanamide was recorded at frequencies from 118 to 649 GHz, which was complemented by measurement of its high-resolution rotation-vibration spectrum at 8-350 cm-1. For D2NCN the analysis revealed considerable perturbations between the lowest Ka rotational energy levels in the 0+ and 0- substates of the lowest inversion doublet. The final data set for D2NCN exceeded 3000 measured transitions and was successfully fitted with a Hamiltonian accounting for the 0+ - 0- coupling. A smaller data set, consisting only of pure rotation and rotation-vibration lines observed with microwave techniques was obtained for HDNCN, and additional transitions of this type were also measured for H2NCN. The spectroscopic data for all three isotopic species were fitted with a unified, robust Hamiltonian allowing confident prediction of spectra well into the terahertz frequency region, which is of interest to contemporary radioastronomy. The isotopic dependence of the determined inversion splitting, -E = 16.4964789(8), 32.089173(3), and 49.567770(6) cm-1, for D2NCN, HDNCN, and H2NCN, respectively, is found to be in good agreement with estimates from a simple reduced quartic-quadratic double minimum potential.

  18. Recombinant human diamine oxidase activity is not inhibited by ethanol, acetaldehyde, disulfiram, diethyldithiocarbamate or cyanamide.

    PubMed

    Bartko, Johann; Gludovacz, Elisabeth; Petroczi, Karin; Borth, Nicole; Jilma, Bernd; Boehm, Thomas

    2016-08-01

    Human diamine oxidase (hDAO, EC 1.4.3.22) is the key enzyme in the degradation of extracellular histamine. Consumption of alcohol is a known trigger of mast cell degranulation in patients with mast cell activation syndrome. Ethanol may also interfere with enzymatic histamine degradation, but reports on the effects on DAO activity are controversial. There are also conflicting reports whether disulfiram, an FDA-approved agent in the treatment of alcohol dependence, inhibits DAO. We therefore investigated the inhibitory potential of ethanol and disulfiram and their metabolites on recombinant human DAO (rhDAO) in three different assay systems. Relevant concentrations of ethanol, acetaldehyde, and acetate did not inhibit rhDAO activity in an in vitro assay system using horseradish peroxidase (HRP) -mediated luminol oxidation. The aldehyde dehydrogenase (ALDH; EC 1.2.1.3) inhibitors cyanamide and its dimer dicyanamide also had no effect on DAO activity. In one assay system, the irreversible ALDH inhibitor disulfiram and its main metabolite diethyldithiocarbamate seemed to inhibit DAO activity. However, the decreased product formation was not due to a direct block of DAO activity but resulted from inhibition of peroxidase employed in the coupled system. Our in vitro data do not support a direct blocking effect of ethanol, disulfiram, and their metabolites on DAO activity in vivo. PMID:27401969

  19. Facile Gold-Catalyzed Heterocyclization of Terminal Alkynes and Cyanamides Leading to Substituted 2-Amino-1,3-Oxazoles.

    PubMed

    Rassadin, Valentin A; Boyarskiy, Vadim P; Kukushkin, Vadim Yu

    2015-07-17

    Facile gold-catalyzed heterocyclization based upon intermolecular trapping of the generated α-oxo gold carbenes with various cyanamides R(2)R(3)NCN (R(2)/R(3) = Alk/Alk, -(CH2)2O(CH2)2-, Ar/Ar, Ar/H) has been developed. In most cases, 2-amino-1,3-oxazoles functionalized at the nitrogen atom as well as at the fifth position of the heterocyclic ring (12 examples) were isolated in good to moderate yields. PMID:26135038

  20. 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. PMID:23179101

  1. 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

    2016-01-01

    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

  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. 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

  4. Inhibition of tomato (Solanum lycopersicum L.) root growth by cyanamide is due to altered cell division, phytohormone balance and expansin gene expression.

    PubMed

    Soltys, Dorota; Rudzińska-Langwald, Anna; Gniazdowska, Agnieszka; Wiśniewska, Anita; Bogatek, Renata

    2012-11-01

    Cyanamide (CA) has been reported as a natural compound produced by hairy vetch (Vicia villosa Roth.) and it was shown also to be an allelochemical, responsible for strong allelopathic potential in this species. CA phytotoxicity has been demonstrated on various plant species, but to date little is known about its mode of action at cellular level. Treatment of tomato (Solanum lycopersicum L.) roots with CA (1.2 mM) resulted in inhibition of growth accompanied by alterations in cell division, and imbalance of plant hormone (ethylene and auxin) homeostasis. Moreover, the phytotoxic effect of CA was also manifested by modifications in expansin gene expression, especially in expansins responsible for cell wall remodeling after the cytokinesis (LeEXPA9, LeEXPA18). Based on these results the phytotoxic activity of CA on growth of roots of tomato seedlings is likely due to alterations associated with cell division. PMID:22847024

  5. The dormancy-breaking stimuli "chilling, hypoxia and cyanamide exposure" up-regulate the expression of α-amylase genes in grapevine buds.

    PubMed

    Rubio, Sebastián; Donoso, Amanda; Pérez, Francisco J

    2014-03-15

    It has been suggested that respiratory stress is involved in the mechanism underlying the dormancy-breaking effect of hydrogen cyanamide (H2CN2) and sodium azide in grapevine buds; indeed, reductions in oxygen levels (hypoxia) and inhibitors of respiration promote bud-break in grapevines. In this study, we showed that, hypoxia increased starch hydrolysis soluble sugar consumption and up-regulated the expression of α-amylase genes (Vvα-AMYs) in grapevine buds, suggesting that these biochemical changes induced by hypoxia, may play a relevant role in the release of buds from endodormancy (ED). Three of the four Vvα-AMY genes that are expressed in grapevine buds were up-regulated by hypoxia and a correlation between changes in sugar content and level of Vvα-AMY gene expression during the hypoxia treatment was found, suggesting that soluble sugars mediate the effect of hypoxia on Vvα-AMY gene expression. Exogenous applications of soluble sugars and sugar analogs confirmed this finding and revealed that osmotic stress induces the expression of Vvα-AMY1 and Vvα-AMY3 and that soluble sugars induces Vvα-AMY2 and Vvα-AMY4 gene expression. Interestingly, the plant hormone gibberellic acid (GA3) induced the expression of Vvα-AMY3 and Vvα-AMY4 genes, while dormancy breaking stimuli, chilling and cyanamide exposure, mainly induced the expression of Vvα-AMY1 and Vvα-AMY2 genes, suggesting that these two α-amylase genes might be involved in the release of grapevine buds from the ED. PMID:24594388

  6. 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.

  7. New cyanate and cyanamide resins as composite matrices

    NASA Technical Reports Server (NTRS)

    Hergenrother, P. M.; Harrison, E. S.; Gosnell, R. B.

    1978-01-01

    The synthesis, polymerization, and laminate properties of two dicyanates, copolymers thereof, and a dicyanamide were studied. The effect of humidity aging (322 K (49 C), 95% relative humidity) and also aging at 505 K (232 C) in circulating air on the RT and elevated temperature properties of HT-S and T-300 unidirectional laminates was determined.

  8. 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...

  9. [Effects of different application rates of calcium cyanamide on soil microbial biomass and enzyme activity in cucumber continuous cropping].

    PubMed

    Zhang, Xue-peng; Ning, Tang-yuan; Yang, Yan; Sun, Tao; Zhang, Shu-min; Wang, Bin

    2015-10-01

    A 2-year field experiment was conducted to study the effects of CaCN2 combined with cucumber straw retention on soil microbial biomass carbon (SMBC) , soil microbial biomass nitrogen (SMBN) and soil enzyme activities under cucumber continuous cropping system. Four treatments were used in this study as follows: CK (null CaCN2), CaCN2-90 (1350 kg CaCN2 . hm-2) CaCN2-60 (900 kg CaCN2 . hm-2), CaCN2-30 (450 kg CaCN2 . hm-2). The results indicated that, compared with the other treatments, CaCN2-90 treatment significantly decreased SMBC in 0-10 cm soil layer at seedling stage, but increased SMBC in 0-20 cm soil layer after early-fruit stage. Compared with CK, CaCN2 increased SMBC in 0-20 cm soil layer at late-fruit stage, and increased SMBN in 0-10 cm soil layer at mid- and late-fruit stages, however there was no significant trend among CaCN2 treatments in the first year (2012), while in the second year (2013) SMBN increased with the increasing CaCN2 amount after mid-fruit stage. CaCN2 increased straw decaying and nutrients releasing, and also increased soil organic matter. Furthermore, the CaCN2-90 could accelerate straw decomposition. Compared with CK, CaCN2 effectively increased soil urease, catalase and polyphenol oxidase activity. The soil urease activity increased while the polyphenol oxidase activity decreased with the increase of CaCN2, and CaCN2-60 could significantly improve catalase activity. Soil organic matter, urease activity and catalase activity had significant positive correlations with SMBC and SMBN. However, polyphenol oxidase activity was negatively correlated to SMBC and SMBN. Our findings indicated that CaCN2 application at 900 kg . hm-2 combined with cucumber straw retention could effectively improve soil environment, alleviating the soil obstacles under the cucumber continuous cropping system. PMID:26995916

  10. The iron-catalyzed construction of 2-aminopyrimidines from alkynenitriles and cyanamides†

    PubMed Central

    Lane, Timothy K.; Nguyen, Minh H.; D'Souza, Brendan R.; Spahn, Nathan A.

    2014-01-01

    Several cycloaddition catalysts and reagents were surveyed for their effectiveness toward cyclizing alkynenitriles with cyanamides. Catalytic amounts of FeI2, iPrPDAI and Zn were found to effectively catalyze the [2+2+2] cycloaddition of a variety of cyanamides and alkynenitriles to afford bicyclic 2-aminopyrimidines. PMID:23877441

  11. HeI photoelectron and theoretical study of the gas phase flash pyrolysis of tetrazole and analysis of CN 2H 2 energy hypersurface

    NASA Astrophysics Data System (ADS)

    Guimon, C.; Khayar, S.; Gracian, F.; Begtrup, M.; Pfister-Guillouzo, G.

    1989-11-01

    The flash thermolysis of tetrazole in vapour phase (1 Pa) is analyzed by HeI photoelectron spectroscopy and quantum calculations (MNDO, ab initio, CI). Experimentally the thermal decomposition of (1H or 2H) tetrazole gives cyanamide (preferentially) and diazomethane. The analysis of the potential energy hypersurface of CN 2H 2 system has enabled the study of the eight possible isomers and the determination of the saddle points between the minima. This study shows that the fact that cyanamide and diazomethane could be observed is due to their thermodynamic stability and the reactivity of different isomers. A lowest energy pathway between tetrazole and cyanamide and diazomethane is proposed.

  12. 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.

  13. 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

  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. The prebiotic synthesis of deoxythymidine oligonucleotides. II - Comparison of condensing agents

    NASA Technical Reports Server (NTRS)

    Odom, D. G.; Brady, J. T.

    1975-01-01

    A reaction which oligomerizes nucleotides under possible prebiotic conditions has been characterized. Nucleoside monophosphate in the presence of cyanamide at acid pH condenses to form dithymidine pyrophosphate and phosphodiester bonded compounds. Imidazole compounds and activated precursors such as nucleoside triphosphate are not necessary for this oligomerization reaction which produces primarily cyclic oligonucleotides.

  17. 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. PMID:24245279

  18. 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}.

  19. 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.

  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. 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.

  2. [Relationships between H2O2 metabolism and Ca2+ transport in dormancy-breaking process of nectarine floral buds].

    PubMed

    Tan, Yue; Gao, Dong-sheng; Li, Ling; Wei, Hai-rong; Wang, Jia-wei; Liu, Qing-zhong

    2015-02-01

    In order to explore regulatory function of H2O2 in bud dormancy release, main effects of three dormancy-breaking treatments (high temperature, hydrogen cyanamide and TDZ) on H2O2 metabolism were determined, and impacts of H2O2 on Ca2+ transport were tested using non-invasive micro-test technique. The results showed that both high temperature and hydrogen cyanamide induced H2O2 accumulation and CAT inhibition were efficient in breaking dormancy during deep dormancy period. However, TDZ showed little impacts on H2O2 metabolism and was much less effective in breaking dormancy. Dormant floral primordium was absorbing state to exogenous Ca2+ due to active calcium channels. The Ca2+ transport could be changed by exogenous H2O2. H2O2 of low concentration reduced the absorption rate of Ca2+, and at high concentration, it changed the Ca2+ transport direction from absorption to release. The results indicated that H2O2 signals were related with Ca2+ signals in dormant buds. Ca2+ signal regulated by H2O2 accumulation might be important in the dormancy-breaking signal transduction process induced by high temperature and hydrogen cyanamide. PMID:26094456

  3. 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.

  4. Plant's sterilization rule for fertile women cited.

    PubMed

    1979-01-01

    The American Cyanamid Corporation has been cited by the Occupational Safety and Health Administration (OSHA) for violating federal law by requiring female employees of childbearing age to be sterilized in order to continue working in areas of the plant where they would be exposed to high levels of airborne lead. High levels of airborne lead can cause damage to workers' reproductive systems and be responsible for birth defects in fetuses. The OSHA charged that American Cyanamid's policy constituted a "willful violation" of the 1970 Occupational Safety and Health Act. The Act requires employers to provide employment that is free from recognized hazards likely to cause death or physical harm. According to OSHA, the Act does not allow an employer to eliminate the hazard by compelling employees to choose between losing their jobs and undergoing sterilization. The reproductive health of workers is considered a valid part of OSHA's regulatory concern. The citation, which carries a $10,000 fine, grew out of a complaint that was filed by the Oil, Chemical and Atomic Workers Union on behalf of 5 female workers working in the lead pigment division of the company's Willow Island, West Virginia plant. The 5 employees alleged that they had themselves sterilized to avoid being transferred to other and possibly lower paying janitorial jobs or losing thier jobs completely. The company is appealing the citation. The union has also filed a complaint with the Equal Employment Opportunity Commission charging American Cyanamid with sex discrimination, since only the women workers are at risk of being transferred to lower paying jobs. PMID:12336913

  5. Analysis of responses to glyceryl trinitrate and sodium nitrite in the intact chest rat.

    PubMed

    Nossaman, Bobby D; Pankey, Edward A; Badejo, Adeleke R; Casey, David B; Uppu, Satvika; Murthy, Subramanyam N; Kadowitz, Philip J

    2012-05-15

    Responses to glyceryl trinitrate/nitroglycerin (GTN), S-nitrosoglutathione (GSNO), and sodium nitrite were compared in the intact chest rat. The iv injections of GTN, sodium nitrite, and GSNO produced dose-dependent decreases in pulmonary and systemic arterial pressures. In as much as cardiac output was not reduced, the decreases in pulmonary and systemic arterial pressures indicate that GTN, sodium nitrite, and GSNO have significant vasodilator activity in the pulmonary and systemic vascular beds in the rat. Responses to GTN were attenuated by cyanamide, but not allopurinol, whereas responses to nitrite formed by the metabolism of GTN were attenuated by allopurinol and cyanamide. The results with allopurinol and cyanamide suggest that only mitochondrial aldehyde dehydrogenase is involved in the bioactivation of GTN, sodium nitrite, and GSNO, whereas both pathways are involved in the bioactivation of nitrite anion in the intact rat. The comparison of vasodilator activity indicates that GSNO and GTN are more than 1000-fold more potent than sodium nitrite in decreasing pulmonary and systemic arterial pressures in the rat. Following administration of 1H-[1,2,4]-oxadizaolo[4,3-]quinoxaline-1-one (ODQ), responses to GTN were significantly attenuated, indicating that responses are mediated by the activation of soluble guanylyl cyclase. These data suggest that the reduction of nitrite to nitric oxide formed from the metabolism of GTN, cannot account for the vasodilator activity of GTN in the intact rat and that another mechanism; perhaps the formation of an S-NO, may mediate the vasodilator response to GTN in this species. PMID:22465477

  6. Analysis of Responses to Glyceryl Trinitrate and Sodium Nitrite in the Intact Chest Rat

    PubMed Central

    Nossaman, Bobby D.; Pankey, Edward A.; Badejo, Adeleke R.; Casey, David B.; Uppu, Satvika; Murthy, Subramanyam N.; Kadowitz, Philip J.

    2012-01-01

    Responses to glyceryl trinitrate/nitroglycerin (GTN), S-nitrosoglutathione (GSNO), and sodium nitrite were compared in the intact chest rat. The iv injections of GTN, sodium nitrite, and GSNO produced dose-dependent decreases in pulmonary and systemic arterial pressures. In as much as cardiac output was not reduced, the decreases in pulmonary and systemic arterial pressures indicate that GTN, sodium nitrite, and GSNO have significant vasodilator activity in the pulmonary and systemic vascular beds in the rat. Responses to GTN were attenuated by cyanamide, but not allopurinol, whereas responses to nitrite formed by the metabolism of GTN were attenuated by allopurinol and cyanamide. The results with allopurinol and cyanamide suggest that only mitochondrial aldehyde dehydrogenase is involved in the bioactivation of GTN, sodium nitrite, and GSNO, whereas both pathways are involved in the bioactivation of nitrite anion in the intact rat. The comparison of vasodilator activity indicates that GSNO and GTN are more than 1000 fold more potent than sodium nitrite in decreasing pulmonary and systemic arterial pressures in the rat. Following administration of 1H-[1,2,4]-oxadizaolo[4,3-]quinoxaline-1-one (ODQ), responses to GTN were significantly attenuated, indicating that responses are mediated by the activation of soluble guanylyl cyclase. These data suggest that the reduction of nitrite to nitric oxide formed from the metabolism of GTN, cannot account for the vasodilator activity of GTN in the intact rat and that another mechanism; perhaps the formation of an S-NO, may mediate the vasodilator response to GTN in this species. PMID:22465477

  7. 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.

  8. 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.

  9. Design aspects of the XV-15 advanced technology blade program

    NASA Technical Reports Server (NTRS)

    Smith, K. E.; Alexander, H. R.; Maisel, M. D.

    1985-01-01

    The paper discusses the design of a tiltrotor blade for application to the XV-15 research demonstration aircraft. The design features 43 deg nonlinear twist and nonuniform tapered planform. The structure is composite with extensive use of graphite in the primary structure. Instrumentation and wiring is encapsulated in the composite structure during the cure cycle. The tip shell is removable, providing access to the tracking and balance weights. This feature provides research facility of alternate tip configurations. The cuff is similarly removable. The graphite epoxy system used is high strain American Cyanamid's Celion 6000ST/Cycom 950. This is the first application of this material in rotor blades.

  10. 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+).

  11. Decarboxylative Palladium(II)-Catalyzed Synthesis of Aryl Amidines from Aryl Carboxylic Acids: Development and Mechanistic Investigation

    PubMed Central

    Rydfjord, Jonas; Svensson, Fredrik; Trejos, Alejandro; Sjöberg, Per J R; Sköld, Christian; Sävmarker, Jonas; Odell, Luke R; Larhed, Mats

    2013-01-01

    A fast and convenient synthesis of aryl amidines starting from carboxylic acids and cyanamides is reported. The reaction was achieved by palladium(II)-catalysis in a one-step microwave protocol using [Pd(O2CCF3)2], 6-methyl-2,2′-bipyridyl and trifluoroacetic acid (TFA) in N-methylpyrrolidinone (NMP), providing the corresponding aryl amidines in moderate to excellent yields. The protocol is very robust with regards to the cyanamide coupling partner but requires electron-rich ortho-substituted aryl carboxylic acids. Mechanistic insight was provided by a DFT investigation and direct ESI-MS studies of the reaction. The results of the DFT study correlated well with the experimental findings and, together with the ESI-MS study, support the suggested mechanism. Furthermore, a scale-out (scale-up) was performed with a non-resonant microwave continuous-flow system, achieving a maximum throughput of 11 mmol h−1 by using a glass reactor with an inner diameter of 3 mm at a flow rate of 1 mL min−1. PMID:23983102

  12. Development of significantly improved catalysts for coal liquefaction and upgrading of coal extracts

    SciTech Connect

    Sinha, V.T.; Kutzenco, P.D.; Preston, W.J.; Brinen, J.S.; Graham, S.W.; Butensky, M.; Muchnick, T.L.; Hyman, D.

    1982-01-01

    During 1979-80, a new generation of very active, long-lived catlaysts for hydrotrating was discovered at the Stamford Research Laboratories of the American Cyanamid Company. The catalysts are based on a unique substrate prepared in bead form from a rehydratable alumina. Their spherical shape, crush strength, and abrasion resistance seem ideally suited for the ebullated bed reactors used in the H-COAL process developed by Hydrocarbon Research, Inc. (HRI). The beads have internal pore structures that are controllable over a wider range than conventional alumina supports, leading to active catalysts that are resistant to poisoning. In September, 1981, the Department of Energy granted a 3-year contract to the American Cyanamid Company for the development of significantly improved catalysts for coal liquefaction anf for upgrading coal extracts, particularly in reactors used in the H-COAL process. Catalysts will first be screened in a batch reactor to identify promising candidated. The latter will be tested in a continuous aging reactor to evaluate their resistance to deactivation under col-liquefaction and extract upgrading conditions. Cold flow ebullation tests of catalysts of different head size are presented, along with some screening and crying of experimental catalysts. Spherical methods for examining catalysts are described.

  13. 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. PMID:12897455

  14. Deprotonated purine dissociation: experiments, computations, and astrobiological implications.

    PubMed

    Cole, Callie A; Wang, Zhe-Chen; Snow, Theodore P; Bierbaum, Veronica M

    2015-01-15

    A central focus of astrobiology is the determination of abiotic formation routes to important biomolecules. The dissociation mechanisms of these molecules lend valuable insights into their synthesis pathways. Because of the detection of organic anions in the interstellar medium (ISM), it is imperative to study their role in these syntheses. This work aims to experimentally and computationally examine deprotonated adenine and guanine dissociation in an effort to illuminate potential anionic precursors to purine formation. Collision-induced dissociation (CID) products and their branching fractions are experimentally measured using an ion trap mass spectrometer. Deprotonated guanine dissociates primarily by deammoniation (97%) with minor losses of carbodiimide (HNCNH) and/or cyanamide (NH2CN), and isocyanic acid (HNCO). Deprotonated adenine fragments by loss of hydrogen cyanide and/or isocyanide (HCN/HNC; 90%) and carbodiimide (HNCNH) and/or cyanamide (NH2CN; 10%). Tandem mass spectrometry (MS(n)) experiments reveal that deprotonated guanine fragments lose additional HCN and CO, while deprotonated adenine fragments successively lose HNC and HCN. Every neutral fragment observed in this study has been detected in the ISM, highlighting the potential for nucleobases such as these to form in such environments. Lastly, the acidity of abundant fragment ions is experimentally bracketed. Theoretical calculations at the B3LYP/6-311++G(d,p) level of theory are performed to delineate the mechanisms of dissociation and analyze the energies of reactants, intermediates, transition states, and products of these CID processes. PMID:25559322

  15. Decarboxylative palladium(II)-catalyzed synthesis of aryl amidines from aryl carboxylic acids: development and mechanistic investigation.

    PubMed

    Rydfjord, Jonas; Svensson, Fredrik; Trejos, Alejandro; Sjöberg, Per J R; Sköld, Christian; Sävmarker, Jonas; Odell, Luke R; Larhed, Mats

    2013-10-01

    A fast and convenient synthesis of aryl amidines starting from carboxylic acids and cyanamides is reported. The reaction was achieved by palladium(II)-catalysis in a one-step microwave protocol using [Pd(O2 CCF3 )2 ], 6-methyl-2,2'-bipyridyl and trifluoroacetic acid (TFA) in N-methylpyrrolidinone (NMP), providing the corresponding aryl amidines in moderate to excellent yields. The protocol is very robust with regards to the cyanamide coupling partner but requires electron-rich ortho-substituted aryl carboxylic acids. Mechanistic insight was provided by a DFT investigation and direct ESI-MS studies of the reaction. The results of the DFT study correlated well with the experimental findings and, together with the ESI-MS study, support the suggested mechanism. Furthermore, a scale-out (scale-up) was performed with a non-resonant microwave continuous-flow system, achieving a maximum throughput of 11 mmol h(-1) by using a glass reactor with an inner diameter of 3 mm at a flow rate of 1 mL min(-1) . PMID:23983102

  16. The Prebiotic Synthesis and Catalytic Role of Imidazoles and Other Condensing Agents

    NASA Astrophysics Data System (ADS)

    Oró, J.; Basile, B.; Cortes, S.; Shen, C.; Yamrom, T.

    1984-12-01

    In the past decade significant advances have been made in the synthesis of oligonucleotides and other polymers by means of imidazoles and other condensing agents. In spite of the current knowledge of the chemistry of imidazoles and their importance as prebiotic catalysts, their formation under primitive earth conditions has not been properly demonstrated. We have now been able to synthesize imidazole as well as its 2-methyl and 4-methyl derivatives under plausible prebiotic conditions. One method utilizes an aldehyde (formaldehyde or acetaldehyde), glyoxal and ammonia as the starting materials for the formation of imidazole and 2-methylimidazole. The other method uses a carbohydrate and ammonia as the key reagents for the synthesis of 4-methylimidazole. The importance of imidazole and related compounds (e.g., cyanamide) in the synthesis of oligonucleotides has been studied by us as well as others. Apparently the charge relay group (-N-C-N-) present in imidazoles, carbodiimides, cyanamide, or the histidine and arginine of enzyme active centers is essential for the synthesis of phosphodiester and pyrophosphate bonds.

  17. N-Co-O Triply Doped Highly Crystalline Porous Carbon: An Acid-Proof Nonprecious Metal Oxygen Evolution Catalyst.

    PubMed

    Yang, Shiliu; Zhan, Yi; Li, Jingfa; Lee, Jim Yang

    2016-02-10

    In comparison with nonaqueous Li-air batteries, aqueous Li-air batteries are kinetically more facile and there is more variety of non-noble metal catalysts available for oxygen electrocatalysis, especially in alkaline solution. The alkaline battery environment is however vulnerable to electrolyte carbonation by atmospheric CO2 resulting in capacity loss over time. The acid aqueous solution is immune to carbonation but is limited by the lack of effective non-noble metal catalysts for the oxygen evolution reaction (OER). This is contrary to the oxygen reduction reaction (ORR) in acid solution where a few good candidates exist. We report here the development of a N-Co-O triply doped carbon catalyst with substantial OER activity in acid solution by the thermal codecomposition of polyaniline, cobalt salt and cyanamide in nitrogen. Cyanamide and the type of cobalt precursor salt were found to determine the structure, crystallinity, surface area, extent of Co doping and consequently the OER activity of the final carbon catalyst in acid solution. We have also put forward some hypotheses about the active sites that may be useful for guiding further work. PMID:26795393

  18. 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.

  19. 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. PMID:26153239

  20. [Pharmacological therapies for alcohol use disorder in Japan].

    PubMed

    Yumoto, Yosuke; Higuchi, Susumu

    2015-09-01

    We reviewed the available pharmacological therapies for alcohol use disorder in Japan. For treatment of withdrawal delirium, therapists prefer to use antipsychotic drugs rather than benzodiazepines, which is different from other countries. Japan does not have any substantial treatment guidelines for withdrawal delirium. Therefore, so treatment strategies matching the environment of each facility need to be formulated. Moreover, current choices for prescribing anti-alcoholic drugs to cope with alcohol craving are limited to drugs such as cyanamide and disulfiram. However, the use of acamprosate has recently begun and a clinical trial for nalmefene is starting soon. We anticipate that these newer pharmacological therapies will contribute to better treatment of alcohol use disorder also in Japan. PMID:26394517

  1. Study and application of molluscicides in Japan*

    PubMed Central

    Komiya, Yoshitaka

    1961-01-01

    For several years after the First World War calcium oxide was the main compound used in the control of Oncomelania nosophora in Japan. This was generally replaced in 1944 by calcium cyanamide; since 1952 the prefectural authorities in areas of endemic bilharziasis have increasingly turned to the use of sodium pentachlorophenate as the molluscicide of choice. Applied at a rate of 5 g per m2, this compound has been found to kill 70%-80% of snails per application. Laboratory and field experiments with calcium-arsenic compounds have been conducted in Japan and have indicated that these products have a relatively high molluscicidal effect; they have, however, not been used on a wide scale for snail control. PMID:14458130

  2. 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

    2016-08-01

    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. PMID:27493184

  3. A New Methodology for the Detection of Low-Abundance Species in the Ism: Detection of Interstellar Carbodiimide (HNCNH)

    NASA Astrophysics Data System (ADS)

    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.

    2013-06-01

    We present the first interstellar detection of carbodiimide (HNCNH) in observations towards Sgr B2(N) using data from the publicly available Green Bank Telescope PRebiotic Interstellar MOlecular Survey project. Recent laboratory work predicts an abundance of HNCNH of ˜10% of the abundance of its tautomer, cyanamide (NH_2CN), or ˜ 2× 10^{13} cm^{-2} in Sgr B2(N). Given this abundance at LTE conditions, the strongest rotational transitions of HNCNH have intensities at or below the noise level of current observations of this source. A thermal population of HNCNH is therefore likely undetectable. Instead, HNCNH is identified via maser emission features at centimeter wavelengths. This detection presents a new methodology for the detection of low-abundance species and further demonstrates the power of cm-wave observations to make definitive identifications based on a small number of observed features.

  4. 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.

  5. 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%.

  6. 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. PMID:26054209

  7. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction

    PubMed Central

    Chung, Hoon T.; Won, Jong H.; Zelenay, Piotr

    2013-01-01

    Nanostructured carbon-based materials, such as nitrogen-doped carbon nanotube arrays, Co3O4/nitrogen-doped graphene hybrids and carbon nanotube–graphene complexes have shown respectable oxygen reduction reaction activity in alkaline media. Although certainly promising, the performance of these materials does not yet warrant implementation in the energy conversion/storage devices utilizing basic electrolytes, for example, alkaline fuel cells, metal-air batteries and certain electrolysers. Here we demonstrate a new type of nitrogen-doped carbon nanotube/nanoparticle composite oxygen reduction reaction electrocatalyst obtained from iron acetate as an iron precursor and from cyanamide as a nitrogen and carbon nanotube precursor in a simple, scalable and single-step method. The composite has the highest oxygen reduction reaction activity in alkaline media of any non-precious metal catalysts. When used at a sufficiently high loading, this catalyst also outperforms the most active platinum-based catalysts. PMID:23715281

  8. 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. PMID:26073846

  9. Value Addition to Sulfate Waste Pickle Liquor of Steel Industry Using Hydrometallurgical Processes

    NASA Astrophysics Data System (ADS)

    Agrawal, Archana; Sahu, K. K.

    2009-12-01

    The solvent extraction of concentrated acid was investigated from sulfate waste pickle liquors using Cyanex 923 (trialkylphosphine oxide (TRPO); manufactured by Cytec Industries Inc., Woodland Park, NJ; provided by Cyanamid Canada Inc. (Markham, Canada)) as an extractant. The effect of various parameters was studied such as extractant concentration, organic-to-aqueous phase ratio, temperature. and retention time on acid extraction from the waste pickle liquor to the organic phase, After the saturation of the organic phase with sulfuric acid, stripping studies were performed to back-extract the pure acid into the aqueous phase. The raffinate of the solvent extraction process that contains both ferrous and ferric iron as well as trace impurities was subjected to oxidation and hydrothermal treatment to precipitate iron with a well-defined pseudo-cubic morphology and a high coercivity value that renders it suitable for high-grade ferrite production.

  10. Intramolecular Aminocyanation of Alkenes via N–CN Bond Cleavage**

    PubMed Central

    Pan, Zhongda; Pound, Sarah M.; Rondla, Naveen R.; Douglas, Christopher J.

    2014-01-01

    A metal-free, Lewis acid-promoted intramolecular aminocyanation of alkenes was developed. B(C6F5)3 activates N-sulfonyl cyanamides, leading an formal cleavage of the N-CN bonds in conjunction with vicinal addition of sulfonamide and nitrile groups across an alkene. This method enables atom-economical access to indolines and tetrahydroquinolines in excellent yields, and provides a complementary strategy for regioselective alkene difunctionalizations with sulfonamide and nitrile groups. Labeling experiments with 13C suggest a fully intramolecular cyclization pattern due to lack of label scrambling in double crossover experiments. Catalysis with Lewis acid is realized and the reaction can be conducted under air. PMID:24719371

  11. Alcohol-induced autophagy contributes to loss in skeletal muscle mass

    PubMed Central

    Thapaliya, Samjhana; Runkana, Ashok; McMullen, Megan R; Nagy, Laura E; McDonald, Christine; Prasad, Sathyamangla V Naga; Dasarathy, Srinivasan

    2014-01-01

    Patients with alcoholic cirrhosis and hepatitis have severe muscle loss. Since ethanol impairs skeletal muscle protein synthesis but does not increase ubiquitin proteasome-mediated proteolysis, we investigated whether alcohol-induced autophagy contributes to muscle loss. Autophagy induction was studied in: A) Human skeletal muscle biopsies from alcoholic cirrhotics and controls, B) Gastrocnemius muscle from ethanol and pair-fed mice, and C) Ethanol-exposed murine C2C12 myotubes, by examining the expression of autophagy markers assessed by immunoblotting and real-time PCR. Expression of autophagy genes and markers were increased in skeletal muscle from humans and ethanol-fed mice, and in myotubes following ethanol exposure. Importantly, pulse-chase experiments showed suppression of myotube proteolysis upon ethanol-treatment with the autophagy inhibitor, 3-methyladenine (3MA) and not by MG132, a proteasome inhibitor. Correspondingly, ethanol-treated C2C12 myotubes stably expressing GFP-LC3B showed increased autophagy flux as measured by accumulation of GFP-LC3B vesicles with confocal microscopy. The ethanol-induced increase in LC3B lipidation was reversed upon knockdown of Atg7, a critical autophagy gene and was associated with reversal of the ethanol-induced decrease in myotube diameter. Consistently, CT image analysis of muscle area in alcoholic cirrhotics was significantly reduced compared with control subjects. In order to determine whether ethanol per se or its metabolic product, acetaldehyde, stimulates autophagy, C2C12 myotubes were treated with ethanol in the presence of the alcohol dehydrogenase inhibitor (4-methylpyrazole) or the acetaldehyde dehydrogenase inhibitor (cyanamide). LC3B lipidation increased with acetaldehyde treatment and increased further with the addition of cyanamide. We conclude that muscle autophagy is increased by ethanol exposure and contributes to sarcopenia. PMID:24492484

  12. Characterization of a new antifungal lipid transfer protein from wheat.

    PubMed

    Kirubakaran, S Isaac; Begum, S Mubarak; Ulaganathan, K; Sakthivel, N

    2008-10-01

    Lipid transfer proteins (LTPs) are members of the family of pathogenesis-related proteins (PR-14) that are believed to be involved in plant defense responses. In this study, a novel gene Ltp 3F1 encoding an antifungal protein from wheat (Sumai 3) was subcloned, overexpressed in Escherichia coli BL-21 (DE3) and enriched using ammonium sulfate fractionation followed by gel permeation chromatography. Molecular phylogeny analyses of wheat Ltp 3F1 gene showed a strong identity to other plant LTPs. Predicted three-dimensional structural model showed the presence of 6 alpha-helices and 9 loop turns. The active site catalytic residues Gly30, Pro50, Ala52 and Cys55 may be suggested for catalyzing the reaction involved in lipid binding. SDS-PAGE analysis confirmed the production of recombinant fusion protein. The LTP fusion protein exhibited a broad-spectrum antifungal activity against Alternaria sp., Rhizoctonia solani, Curvularia lunata, Bipolaris oryzae, Cylindrocladium scoparium, Botrytis cinerea and Sarocladium oryzae. Gene cassette with cyanamide hydratase (cah) marker and Ltp 3F1 gene was constructed for genetic transformation in tobacco. Efficient regeneration was achieved in selective media amended with cyanamide. Transgenic plants with normal phenotype were obtained. Results of PCR and Southern, Northern and Western hybridization analyses confirmed the integration and expression of genes in transgenic plants. Experiments with detached leaves from transgenic tobacco expressing Ltp 3F1 gene showed fungal resistance. Due to the innate potential of broad-spectrum antifungal activity, wheat Ltp 3F1 gene can be used to enhance resistance against fungi in crop plants. PMID:18595724

  13. 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.

  14. Synthesis of novel solid materials from carbon dioxide and carbon monoxide

    NASA Astrophysics Data System (ADS)

    Huo, Yan

    generate carbon nitride and lithium cyanamide. Furthermore, the thermodynamic calculation indicated that the reaction between carbon monoxide and lithium imide can produce graphone and lithium cyanamide along with releasing heat. Based on the above thermodynamic analysis, the experiment of CO 2 and Li3N reaction and CO and Li2NH were carried out. It was found that the reaction between CO2 and Li3N is very fast and exothermic. The XRD and element analysis revealed that the products are crystal lithium cyanamide and amorphous carbon nitrides with Li2O and Li2CO3. Furthermore, TEM images showed that carbon nitrides possess layer-structure, namely, it is graphene-structured carbon nitride. It was found that the reaction between Li2NH and CO was also exothermic, which produced graphone instead of carbon nitride. The composition and structures of graphone were evaluated by XRD, element analysis, TEM observation, and Raman spectra.

  15. 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

  16. 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

  17. 2-pyrazinylnitrene and 4-pyrimidylnitrene. Ring expansion to 1,3,5-triazacyclohepta-1,2,4,6-tetraene and ring opening to (2-Isocyanovinyl)carbodiimide.

    PubMed

    Addicott, Chris; Wong, Ming Wah; Wentrup, Curt

    2002-11-29

    Tetrazolo[1,5-a]pyrazine/2-azidopyrazine 9T/9A undergo photolysis in Ar matrix at cryogenic temperatures to yield 1,3,5-triazacyclohepta-1,2,4,6-tetraene 21 as the first observable intermediate, and 1-cyanoimidazole 11 and (2-isocyanovinyl)carbodiimide 22 as the final products. The latter tautomerizes to 2-(isocyanovinyl)cyanamide 23 on warming to 40 K. The same intermediate 21 and the same final products are obtained on matrix photolysis of the isomeric tetrazolo[1,5-c]pyrimidine/4-azidopyrimidine 24T/24A. These photolysis results as well as those of the previously reported thermal ring contraction of (15)N-labeled 2-pyrazinyl- and 4-pyrimidylnitrenes to 1-cyanoimidazoles can all be rationalized in terms of selective ring opening of 21 or nitrine 10 to a nitrile ylide zwitterion 28 prior to formation of the final products, 11 and 22. The results are supported by high-level ab initio and DFT calculations (CASPT2-CASSCF(6,6), G3(MP2), and B3LYP/6-31+G) of the energies and IR spectra of the intermediates and products. PMID:12444636

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

    PubMed

    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

  19. Studies on precellular evolution: The encapsulation of polyribonucleotides by liposomes

    NASA Astrophysics Data System (ADS)

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

    Liposomes are 5 to 50 micron vesicles with an internal aqueous environment, whose amphiphilic lipidic components self-assemble into systems with at least one double-layered membrane. Liposomes have been suggested as possible models of precellular systems formed in the early Archean Earth from lipids of non-enzymatic origin. Since it is generally accepted that RNA molecules preceded double-stranded DNA molecules as genetic material, we have studied the encapsulation of polyribonucleotides within liposomes made from dipalmitoyl phosphatidylcholine, and from egg yolk phosphatidylcholine to which cholesterol was added in some cases. The liposomes were prepared under anoxic conditions following the reverse phase evaporation method described by Szoka and Papahadjopoulos /1/. Quantitative determinations show that approximately 50% of the available lipids form liposomes, and that up to 5% of the polyribonucleotides can be entrapped by them. We have also studied the encapsulation of polyribonucleotides in the presence of 1) urea and cyanamide, two non-electrolytes that have been used as prebiotic condensing agents, and 2) of Zn++ and Pb++, two cations employed in the non-enzymatic template-directed synthesis of polyribonucleotides from activated nucleotides.

  20. 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.

  1. Differential phosphorylation of translation initiation regulators 4EBP1, S6k1, and Erk 1/2 following inhibition of alcohol metabolism in mouse heart.

    PubMed

    Vary, Thomas C; Lang, Charles H

    2008-03-01

    Acute alcohol intoxication leads to an inhibition of protein synthesis in heart that results in part through altered phosphorylation of protein factors controlling mRNA translation initiation. The purpose of the present set of experiments was designed to examine the effects of inhibitors of ethanol metabolism on the phosphorylation of 4E-binding protein (4EBP1) and S6k1(Thr(389)), two factors regulating mRNA translation initiation. Phosphorylation of 4E-BP1, S6k1(Thr(389)), and Erk 1/2 was reduced 2 h following IP injection of alcohol. Pretreatment with 4-methylpyrazole (4-MP), an inhibitor of alcohol dehydrogenase (ADH), did not attenuate the ethanol-induced decrease in phosphorylation of 4EBP1 and S6k1(Thr(389)). In contrast, 4-MP prevented the decrease in Erk 1/2 phosphorylation observed with acute ethanol intoxication. Pretreatment with cyanamide, an inhibitor of aldehyde dehydrogenase, did not attenuate the ethanol-induced decrease in phosphorylation S6k1(Thr(389)), but partially prevented the ethanol-induced lowering of 4EBP1 phosphorylation. The studies indicate that modulation of ethanol metabolism through inhibition of ADH or aldehyde dehydrogenase leads to preferential modulation of the phosphorylation of distinct myocardial signaling systems involved in regulating protein synthesis. PMID:18317950

  2. Evidence for the generation of transaminase inhibitor(s) during ethanol metabolism by rat liver homogenates: a potential mechanism for alcohol toxicity.

    PubMed

    Solomon, L R

    1987-08-01

    Since ethanol consumption decreases hepatic aminotransferase activities in vivo, mechanisms of ethanol-mediated transaminase inhibition were explored in vitro using mitochondria-depleted rat liver homogenates. When homogenates were incubated at 37 degrees with 50 mM ethanol for 1 hr, alanine aminotransferase decreased by 20%, while aspartate aminotransferase was unchanged. After 2 hr, aspartate aminotransferase decreased by 20% and by 3 hr, alanine and aspartate aminotransferases were decreased by 31 and 23%, respectively. Levels of acetaldehyde generated during ethanol oxidation were 525 +/- 47 microM at 1 hr, 855 +/- 14 microM at 2 hr, and 1293 +/- 140 microM at 3 hr. Although inhibition of alcohol oxidation with methylpyrazole or cyanide markedly decreased ethanol-mediated transaminase inhibition, neither incubation with acetate nor generation of reducing equivalents by oxidation of lactate, malate, xylitol, or sorbitol altered the activity of either enzyme. However, semicarbazide, an aldehyde scavenger, prevented inhibition of both aminotransferases by ethanol. Moreover, incubation with 5 mM acetaldehyde for 1 hr inhibited alanine and aspartate aminotransferases by 36 and 26%, respectively. Cyanamide, an aldehyde dehydrogenase inhibitor, had little effect on ethanol-mediated transaminase inhibition. Thus, metabolism of ethanol by rat liver homogenates produces transaminase inhibition similar to that described in vivo and this effect requires acetaldehyde generation but not acetaldehyde oxidation. Since addition of pyridoxal 5'-phosphate to assay mixes did not reverse ethanol effects, aminotransferase inhibition does not result from displacement of vitamin B6 coenzymes. PMID:3663401

  3. Studies on the mechanism of acetaldehyde-mediated inhibition of rat liver transaminases.

    PubMed

    Solomon, L R

    1987-09-30

    Incubation of mitochondria-depleted rat liver homogenates with 5 mmol/l acetaldehyde at 37 degrees C for 1 h inhibited both aspartate and alanine aminotransferases by 30%. Inhibition was prevented by decreasing temperature to 4 degrees C or by preincubating homogenates with cyanate but was unaffected by cyanamide and methylpyrazole which block acetaldehyde oxidation and reduction respectively. Cyanate-sensitive acetaldehyde-mediated inhibition of purified porcine heart transaminases was also demonstrated in the presence of rat liver homogenate but not in Tris/sucrose medium. Moreover, porcine transaminases were inhibited by trichloroacetic acid extracts of rat liver homogenates previously incubated with acetaldehyde but not by extracts of homogenates incubated with both acetaldehyde and cyanate. These findings suggest that acetaldehyde-mediated transaminase inhibition requires further non-oxidative metabolism of acetaldehyde. Since transaminase activities were not restored by addition of pyridoxal 5'-phosphate to the assay systems, acetaldehyde-induced transaminase inhibition does not appear to be mediated by displacement or depletion of this B6 coenzyme. PMID:3677417

  4. Selective derivatization and sequestration of ribose from a prebiotic mix.

    PubMed

    Springsteen, Greg; Joyce, Gerald F

    2004-08-11

    Observations regarding the catalytic potential of RNA and the role of RNA in biology have formed the basis for the "RNA world" hypothesis, which suggests that a genetic system based on self-replicating polyribonucleotides preceded modern biology. However, attempts to devise a realistic prebiotic synthesis of nucleic acids from simple starting materials have been plagued by problems of poor chemical selectivity, lack of stereo- and regiospecificity, and similar rates of formation and degradation of some of the key intermediates. For example, ribose would have been only a small component of a highly complex mix of sugars resulting from the condensation of formaldehyde in a prebiotic world. In addition, ribose is more reactive and degrades more rapidly compared with most other monosaccharides. This study demonstrates an approach for the preferential sequestration of ribose relative to other sugars that takes advantage of its greater reactivity. Cyanamide reacts especially rapidly with ribose to form a stable bicyclic adduct. This product crystallizes spontaneously in aqueous solution, whereas the corresponding products derived from threose, galactose, glucose, mannose, and each of the other pentoses do not. Furthermore, when employing a racemic mixture of d- and l-ribose, enantiomerically twinned crystals are formed that contain discrete homochiral domains. PMID:15291561

  5. 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.

  6. 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.

  7. 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.

  8. Novel access to azaphosphiridine complexes and first applications using Brønsted acid-induced ring expansion reactions.

    PubMed

    Fankel, Stefan; Helten, Holger; von Frantzius, Gerd; Schnakenburg, Gregor; Daniels, Jörg; Chu, Victoria; Müller, Christina; Streubel, Rainer

    2010-04-14

    Synthesis of azaphosphiridine complexes 3a-e was achieved via thermal group transfer reaction using 2H-azaphosphirene complex 1 and N-methyl C-aryl imines 2a-e (i) or via reaction of transient Li/Cl phosphinidenoid complex 5 (prepared from dichloro(organo)phosphane complex 4) using 2a-c (ii), respectively. Reaction of complexes 3a,d and trifluoromethane sulfonic acid in the presence of dimethyl cyanamide led to a highly bond- and regioselective ring expansion yielding 1,3,4sigma3lambda3-diazaphosphol-2-ene complexes 8a,d after deprotonation with NEt3. 31P NMR reaction monitoring revealed that protonation of complex 3a yields the azaphosphiridinium complex 6a, unambiguously identified by NMR spectroscopy at low temperature. All isolated products were characterized by multinuclear NMR spectroscopy, IR and UV/Vis (for 3a,d, 6a, 8a,d), MS and single-crystal X-ray crystallography in the cases of complexes 3b-d, 8a and 8d. DFT studies on the reaction mechanism and compliance constants of the model complex of 6a are presented. PMID:20379537

  9. Synthesis and crystal structure of cubic Ca16Si17N34.

    PubMed

    Hick, Sandra M; Miller, Mattheu I; Kaner, Richard B; Blair, Richard G

    2012-12-01

    Since the late 1960s, the exact structure of cubic calcium silicon nitride has been a source of debate. This paper offers evidence that the cubic phase CaSiN(2) described in the literature is actually Ca(16)Si(17)N(34). Presented here is a method for synthesizing single crystals of cubic-calcium silicon nitride from calcium nitride and elemental silicon under flowing nitrogen at 1500 °C. The colorless millimeter-sized crystals of Ca(16)Si(17)N(34) with a refractive index (n(25)) = 1.590 were found to be cubic (a = 14.8882 Å) and belong to the space group F43m (216). The synthesis of bulk, powdered cubic-Ca(16)Si(17)N(34) from calcium cyanamide and silicon is also discussed. Ca(16)Si(17)N(34) is a relatively air-stable refractory ceramic. In contrast to the orthorhombic phase of CaSiN(2), in which Ca(2+) sits in octahedral sites, this cubic phase has Ca(2+) in cubic sites that makes it an interesting host for new phosphors and gives rise to unique crystal field splitting. PMID:23157279

  10. 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.

  11. 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.

  12. High-temperature Adhesive Development and Evaluation

    NASA Technical Reports Server (NTRS)

    Hendricks, C. L.; Hale, J. N.

    1985-01-01

    High-temperature adhesive systems are evaluated for short and long-term stability at temperatures ranging from 232C to 427C. The resins selected for characterization include: NASA Langley developed polyphenylquinoxaline (PPQ), and commercially available polyimides (PI). The primary method of bond testing is single lap shear. The PPQ candidates are evaluated on 6A1-4V titanium adherends with chromic acid anodize and phosphate fluoride etch surface preparations. The remaining adhesives are evaluated on 15-5 PH stainless steel with a sulfuric acid anodize surface preparation. Preliminary data indicate that the PPQ adhesives tested have stability to 3000 hours at 450F with chromic acid anodize surface preparation. Additional studies are continuing to attempt to improve the PPQ's high-performance by formulating adhesive films with a boron filler and utilizing the phosphate fluoride surface preparation on titanium. Evaluation of the polyimide candidates on stainless-steel adherends indicates that the FM-35 (American Cyanamid), PMR-15 (U.S. Polymeric/Ferro), TRW partially fluorinated polyimide and NR 150B2S6X (DuPont) adhesives show sufficient promise to justify additional testing.

  13. 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.

  14. 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.

  15. 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

  16. Ethanol-induced impairment of hepatic glycoprotein secretion in the isolated rat liver perfusion model

    SciTech Connect

    Volentine, G.D.; Ogden, K.A.; Tuma, D.J.; Sorrell, M.F.

    1987-05-01

    The authors have previously shown that acute administration of ethanol inhibits hepatic glycoprotein secretion in vivo. This ethanol-induced effect appears to be mediated by its reactive metabolite, acetaldehyde. Since hormonal influences and vascular changes can not be controlled in vivo during ethanol administration, they investigated the effect of ethanol in the isolated perfused liver model. Rat liver from fed animals was perfused with oxygenated KRB at 3 ml/min/g liver for 4 hrs. Since ethanol inhibits proteins synthesis in vitro, protein acceptor pool size was equalized in both ethanol and control perfused livers with 1 mM cycloheximide. /sup 3/H-glucosamine was used to label hepatic secretory glycoproteins in the perfusate. Colchicine, a known inhibitor of protein secretion, impaired the secretion of labeled glycoproteins with a concomitant retention of these export proteins in the liver; therefore, confirming the authors secretory model. Ethanol (50 mM) inhibited the appearance of glucosamine-labeled glycoproteins by 60% into the perfusate as compared to control livers. Pretreatment of animals with cyanamide (an aldehyde dehydrogenase inhibitor) further potentiated this effect of ethanol in the isolated perfused liver. These data suggest that ethanol inhibits hepatic glycoprotein secretion in the isolated liver perfusion model, and this ethanol-induced impairment appears to be mediated by acetaldehyde.

  17. 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.

  18. 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

  19. Exploration and pharmacokinetic profiling of phenylalanine based carbamates as novel substance p 1-7 analogues.

    PubMed

    Fransson, Rebecca; Nordvall, Gunnar; Bylund, Johan; Carlsson-Jonsson, Anna; Kratz, Jadel M; Svensson, Richard; Artursson, Per; Hallberg, Mathias; Sandström, Anja

    2014-12-11

    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

  20. Detection of Potential TNA and RNA Nucleoside Precursors in a Prebiotic Mixture by Pure Shift Diffusion-Ordered NMR Spectroscopy

    PubMed Central

    Islam, Saidul; Aguilar, Juan A; Powner, Matthew W; Nilsson, Mathias; Morris, Gareth A; Sutherland, John D

    2013-01-01

    In the context of prebiotic chemistry, one of the characteristics of mixed nitrogenous-oxygenous chemistry is its propensity to give rise to highly complex reaction mixtures. There is therefore an urgent need to develop improved spectroscopic techniques if onerous chromatographic separations are to be avoided. One potential avenue is the combination of pure shift methodology, in which NMR spectra are measured with greatly improved resolution by suppressing multiplet structure, with diffusion-ordered spectroscopy, in which NMR signals from different species are distinguished through their different rates of diffusion. Such a combination has the added advantage of working with intact mixtures, allowing analyses to be carried out without perturbing mixtures in which chemical entities are part of a network of reactions in equilibrium. As part of a systems chemistry approach towards investigating the self-assembly of potentially prebiotic small molecules, we have analysed the complex mixture arising from mixing glycolaldehyde and cyanamide, in a first application of pure shift DOSY NMR to the characterisation of a partially unknown reaction composition. The work presented illustrates the potential of pure shift DOSY to be applied to chemistries that give rise to mixtures of compounds in which the NMR signal resolution is poor. The direct formation of potential RNA and TNA nucleoside precursors, amongst other adducts, was observed. These preliminary observations may have implications for the potentially prebiotic assembly chemistry of pyrimidine threonucleotides, and therefore of TNA, by using recently reported chemistries that yield the activated pyridimidine ribonucleotides. PMID:23371787

  1. Synthesis, Molecular Structure, Metabolic Stability and QSAR Studies of a Novel Series of Anticancer N-Acylbenzenesulfonamides.

    PubMed

    Żołnowska, Beata; Sławiński, Jarosław; Belka, Mariusz; Bączek, Tomasz; Kawiak, Anna; Chojnacki, Jarosław; Pogorzelska, Aneta; Szafrański, Krzysztof

    2015-01-01

    A series of novel N-acyl-4-chloro-5-methyl-2-(R¹-methylthio)benzenesulfonamides 18-47 have been synthesized by the reaction of N-[4-chloro-5-methyl-2-(R¹-methylthio) benzenesulfonyl]cyanamide potassium salts with appropriate carboxylic acids. Some of them showed anticancer activity toward the human cancer cell lines MCF-7, HCT-116 and HeLa, with the growth percentages (GPs) in the range from 7% to 46%. Quantitative structure-activity relationship (QSAR) studies on the cytotoxic activity of N-acylsulfonamides toward MCF-7, HCT-116 and HeLa were performed by using topological, ring and charge descriptors based on the stepwise multiple linear regression technique (MLR). The QSAR studies revealed three predictive and statistically significant models for the investigated compounds. The results obtained with these models indicated that the anticancer activity of N-acylsulfonamides depends on topological distances, number of ring system, maximum positive charge and number of atom-centered fragments. The metabolic stability of the selected compounds had been evaluated on pooled human liver microsomes and NADPH, both R¹ and R² substituents of the N-acylsulfonamides simultaneously affected them. PMID:26506328

  2. Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride).

    PubMed

    Hanusek, Jirí; Russell, Mark A; Laws, Andrew P; Jansa, Petr; Atherton, John H; Fettes, Kevin; Page, Michael I

    2007-02-01

    Contrary to a previous report, the sulfurisation of phosphorus(III) derivatives by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products. The reaction of xanthane hydride with triphenyl phosphine or trimethyl phosphite yields triphenyl phosphine sulfide or trimethyl thiophosphate, respectively, and thiocarbamoyl isothiocyanate which has been trapped with nucleophiles. The reaction pathway involves initial nucleophilic attack of the phosphorus at sulfur next to the thiocarbonyl group of xanthane hydride followed by decomposition of the phosphonium intermediate formed to products. The Hammett rho-values for the sulfurisation of substituted triphenyl phosphines and triphenyl phosphites in acetonitrile are approximately -1.0. The entropies of activation are very negative (-114+/-15 J mol-1 K-1) with little dependence on solvent which is consistent with a bimolecular association step leading to the transition state. The negative values of DeltaS(not equal) and rho values indicate that the rate limiting step of the sulfurisation reaction is formation of the phosphonium ion intermediate which has an early transition state with little covalent bond formation. The site of nucleophilic attack has been also confirmed using computational calculations. PMID:17252130

  3. Isoflurane Preconditioning Confers Cardioprotection by Activation of ALDH2

    PubMed Central

    Lang, Xiao-E; Wang, Xiong; Zhang, Ke-Rang; Lv, Ji-Yuan; Jin, Jian-Hua; Li, Qing-Shan

    2013-01-01

    The volatile anesthetic, isoflurane, protects the heart from ischemia/reperfusion (I/R) injury. Aldehyde dehydrogenase 2 (ALDH2) is thought to be an endogenous mechanism against ischemia-reperfusion injury possibly through detoxification of toxic aldehydes. We investigated whether cardioprotection by isoflurane depends on activation of ALDH2.Anesthetized rats underwent 40 min of coronary artery occlusion followed by 120 min of reperfusion and were randomly assigned to the following groups: untreated controls, isoflurane preconditioning with and without an ALDH2 inhibitor, the direct activator of ALDH2 or a protein kinase C (PKCε) inhibitor. Pretreatment with isoflurane prior to ischemia reduced LDH and CK-MB levels and infarct size, while it increased phosphorylation of ALDH2, which could be blocked by the ALDH2 inhibitor, cyanamide. Isolated neonatal cardiomyocytes were treated with hypoxia followed by reoxygenation. Hypoxia/reoxygenation (H/R) increased cardiomyocyte apoptosis and injury which were attenuated by isoflurane and forced the activation of ALDH2. In contrast, the effect of isoflurane-induced protection was almost abolished by knockdown of ALDH2. Activation of ALDH2 and cardioprotection by isoflurane were substantially blocked by the PKCε inhibitor. Activation of ALDH2 by mitochondrial PKCε plays an important role in the cardioprotection of isoflurane in myocardium I/R injury. PMID:23468836

  4. 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.

  5. 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. PMID:20652990

  6. Solid-Phase Synthesis of 1,3,7,8-Tetrasubstituted Xanthine Derivatives on Traceless Solid Support.

    PubMed

    Lee, Doohyun; Lee, Seungyeon; Liu, Kwang-Hyeon; Bae, Jong-Sup; Baek, Dong Jae; Lee, Taeho

    2016-01-11

    Traceless solid-phase synthesis of 1,3,7,8-tetrasubstituted xanthine (1,3,7,8-tetrasubstituted 1H-purine-2,6(3H,7H)-dione) derivatives has been developed. The solid-phase synthetic route began on a solid supported N'-cyano-N-substituted carbamimidothioate, which was prepared from cyanamide, isothiocyanate, and Merrifield resin. After N-alkylation of carbamimidothioate resin with ethyl 2-bromoacetate, an imidazole ring is introduced by Thorpe-Ziegler-type cyclization. The resulting imidazole resin is converted to 1,3,7-trisubstituted xanthine resin using sequential reactions, such as Lewis acid-catalyzed urea formation, pyrimidine ring cyclization, and N-alkylation. After oxidation of sulfides to sulfones, traceless cleavage with amine or thiol nucleophiles afforded the desired 1,3,7,8-tetrasubstituted xanthines in good purities and overall yields (eight-steps; 36 examples). This efficient solid-phase synthesis enables the incorporation of four diversity points into the preparation of the 1,3,7,8-tetrasubstituted xanthines. PMID:26616892

  7. Influence of Avotan on the microflora and concentrations of ammonia and volatile fatty acids in the rumen.

    PubMed

    Sommer, A; Chrenková, M; Ceresnáková, Z; Szakács, J; Flák, P; Uváciková, I

    1993-01-01

    The influence of Avotan (Firm Cyanamid) was studied on VFA concentration, pH, dynamics of NH3 and on numbers of chosen species of rumen microorganisms in physiological experiments with four young bulls and two wethers with rumen cannulas. It was found no marked physiological change in pH of rumen fluid under the influence of Avotan. Difference between groups were statistical significant. Avotan caused significant (P < or = 0.01) decrease of molar % of acetic acid (from 67.0 to 62.1) and an increase of propionic acid (from 16.41 to 28.21 mol %) in wethers. These changes were nonsignificant with bulls. The acetate: propionate ratio decreased significantly from 4.1 to 2.2 in wethers. Avotan decreased highly significantly (P < or = 0.01) the level of NH3 in the rumen fluid during the observed period (0, 1.5, 3, 4.5 and 6 hours after feeding) in bulls. It was observed the similar effect in wethers 3 hours after feeding (from 170 mmol to 81 mmol/l). Decrease of the total number of microorganisms in the rumen fluid was observed in animals which received Avotan (on the average 3.5 times in young bulls, and 4.5 times in wethers). The number of enterococci decreased significantly (2.8-4.5 times), number of amylolytic bacteria decreased less significantly. PMID:8572917

  8. 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.

  9. Mitochondrial aldehyde dehydrogenase mediates vasodilator responses of glyceryl trinitrate and sodium nitrite in the pulmonary vascular bed of the rat.

    PubMed

    Badejo, Adeleke M; Hodnette, Chris; Dhaliwal, Jasdeep S; Casey, David B; Pankey, Edward; Murthy, Subramanyam N; Nossaman, Bobby D; Hyman, Albert L; Kadowitz, Philip J

    2010-09-01

    It has been reported that mitochondrial aldehyde dehydrogenase (ALDH2) catalyzes the formation of glyceryl dinitrate and inorganic nitrite from glyceryl trinitrate (GTN), leading to an increase in cGMP and vasodilation in the coronary and systemic vascular beds. However, the role of nitric oxide (NO) formed from nitrite in mediating the response to GTN in the pulmonary vascular bed is uncertain. The purpose of the present study was to determine if nitrite plays a role in mediating vasodilator responses to GTN. In this study, intravenous injections of GTN and sodium nitrite decreased pulmonary and systemic arterial pressures and increased cardiac output. The decreases in pulmonary arterial pressure under baseline and elevated tone conditions and decreases in systemic arterial pressure in response to GTN and sodium nitrite were attenuated by cyanamide, an ALDH2 inhibitor, whereas responses to the NO donor, sodium nitroprusside (SNP), were not altered. The decreases in pulmonary and systemic arterial pressure in response to GTN and SNP were not altered by allopurinol, an inhibitor of xanthine oxidoreductase, whereas responses to sodium nitrite were attenuated. GTN was approximately 1,000-fold more potent than sodium nitrite in decreasing pulmonary and systemic arterial pressures. These results suggest that ALDH2 plays an important role in the bioactivation of GTN and nitrite in the pulmonary and systemic vascular beds and that the reduction of nitrite to vasoactive NO does not play an important role in mediating vasodilator responses to GTN in the intact chest rat. PMID:20543077

  10. Mitochondrial aldehyde dehydrogenase mediates vasodilator responses of glyceryl trinitrate and sodium nitrite in the pulmonary vascular bed of the rat

    PubMed Central

    Badejo, Adeleke M.; Hodnette, Chris; Dhaliwal, Jasdeep S.; Casey, David B.; Pankey, Edward; Murthy, Subramanyam N.; Nossaman, Bobby D.; Hyman, Albert L.

    2010-01-01

    It has been reported that mitochondrial aldehyde dehydrogenase (ALDH2) catalyzes the formation of glyceryl dinitrate and inorganic nitrite from glyceryl trinitrate (GTN), leading to an increase in cGMP and vasodilation in the coronary and systemic vascular beds. However, the role of nitric oxide (NO) formed from nitrite in mediating the response to GTN in the pulmonary vascular bed is uncertain. The purpose of the present study was to determine if nitrite plays a role in mediating vasodilator responses to GTN. In this study, intravenous injections of GTN and sodium nitrite decreased pulmonary and systemic arterial pressures and increased cardiac output. The decreases in pulmonary arterial pressure under baseline and elevated tone conditions and decreases in systemic arterial pressure in response to GTN and sodium nitrite were attenuated by cyanamide, an ALDH2 inhibitor, whereas responses to the NO donor, sodium nitroprusside (SNP), were not altered. The decreases in pulmonary and systemic arterial pressure in response to GTN and SNP were not altered by allopurinol, an inhibitor of xanthine oxidoreductase, whereas responses to sodium nitrite were attenuated. GTN was ∼1,000-fold more potent than sodium nitrite in decreasing pulmonary and systemic arterial pressures. These results suggest that ALDH2 plays an important role in the bioactivation of GTN and nitrite in the pulmonary and systemic vascular beds and that the reduction of nitrite to vasoactive NO does not play an important role in mediating vasodilator responses to GTN in the intact chest rat. PMID:20543077

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

    NASA Technical Reports Server (NTRS)

    Scialdone, John J.

    1989-01-01

    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.

  13. Facile fabrication of novel SiO2/g-C3N4 core-shell nanosphere photocatalysts with enhanced visible light activity

    NASA Astrophysics Data System (ADS)

    Lin, Bo; Xue, Chao; Yan, Xiaoqing; Yang, Guidong; Yang, Guang; Yang, Bolun

    2015-12-01

    Novel SiO2/g-C3N4 core-shell nanospheres were simply synthesized using heating method to anneal the mixture of silica dioxide nanospheres and molten cyanamide (CA) in nitrogen atmosphere. The effects of various initial mass ratios of SiO2 nanospheres and CA molecules on the catalyst structure, surface property and catalytic activity have been systematically investigated. The characterization results show that the as-obtained photocatalysts possess the ordered core-shell nanostructure, large mesoporous distribution and inflated BET specific surface areas. The photocatalytic activities of the SiO2/g-C3N4 composites were evaluated by decomposing the rhodamine B (RhB) dye under visible light irradiation. Compared with pure g-C3N4, all of the SiO2/g-C3N4 core-shell composites showed the improved photoactivity, and the optimal SiO2/g-C3N4 catalyst (SC-3) showed the highest activity with an RhB conversion of 94.3% after 150 min visible light irradiation, which is 3.5 times higher than that of pure g-C3N4. Meanwhile, the recycling test showed that the SC-3 sample owns outstanding stability and durability. The enhancement in both activity and stability can be assigned to the specific core-shell structure, inflated surface area, higher visible light adsorption and efficient charge separation originating from the closely contacted interfaces between SiO2 nanospheres and g-C3N4.

  14. 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.

  15. Cytochromes P450 Catalyze the Reduction of α,β-Unsaturated Aldehydes

    PubMed Central

    Amunom, Immaculate; Dieter, Laura J.; Tamasi, Viola; Cai, Jan; Conklin, Daniel J.; Srivastava, Sanjay; Martin, Martha V.; Guengerich, F. Peter; Prough, Russell A.

    2011-01-01

    The metabolism of α,β-unsaturated aldehydes, e.g. 4-hydroxynonenal, involves oxidation to carboxylic acids, reduction to alcohols, and glutathionylation to eventually form mercapturide conjugates. Recently we demonstrated that P450s can oxidize aldehydes to carboxylic acids, a reaction previously thought to involve aldehyde dehydrogenase. When recombinant cytochrome P450 3A4 was incubated with 4-hydroxynonenal, O2, and NADPH, several products were produced, including 1,4-dihydroxynonene (DHN), 4-hydroxy-2-nonenoic acid (HNA), and an unknown metabolite. Several P450s catalyzed the reduction reaction in the order (human) P450 2B6 ≅ P450 3A4 > P450 1A2 > P450 2J2 > (mouse) P450 2c29. Other P450s did not catalyze the reduction reaction (human P450 2E1 & rabbit P450 2B4). Metabolism by isolated rat hepatocytes showed that HNA formation was inhibited by cyanamide, while DHN formation was not affected. Troleandomycin increased HNA production 1.6-fold while inhibiting DHN formation, suggesting that P450 3A11 is a major enzyme involved in rat hepatic clearance of 4-HNE. A fluorescent assay was developed using 9-anthracenealdehyde to measure both reactions. Feeding mice diet containing t-butylated hydroxyanisole increased the level of both activities with hepatic microsomal fractions, but not proportionally. Miconazole (0.5 mM) was a potent inhibitor of these microsomal reduction reactions, while phenytoin and α-naphthoflavone (both at 0.5 mM) were partial inhibitors, suggesting the role of multiple P450 enzymes. The oxidative metabolism of these aldehydes was inhibited >90% in an Ar or CO atmosphere, while the reductive reactions were not greatly affected. These results suggest that P450s are significant catalysts of reduction of α,β-unsaturated aldehydes in liver. PMID:21766881

  16. 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

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

    PubMed

    Abernethy, Grant; Higgs, Kerianne

    2013-05-01

    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. PMID:23540766

  18. 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

  19. 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

  20. 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. PMID:26940832

  1. 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. PMID:27337491

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

    PubMed

    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. Nitrile imines: matrix isolation, IR spectra, structures, and rearrangement to carbodiimides.

    PubMed

    Bégué, Didier; Qiao, Greg GuangHua; Wentrup, Curt

    2012-03-21

    The structures and reactivities of nitrile imines are subjects of continuing debate. Several nitrile imines were generated photochemically or thermally and investigated by IR spectroscopy in Ar matrices at cryogenic temperatures (Ph-CNN-H 6, Ph-CNN-CH(3)17, Ph-CNN-SiMe(3)23, Ph-CNN-Ph 29, Ph(3)C-CNN-CPh(3)34, and the boryl-CNN-boryl derivative 39). The effect of substituents on the structures and IR absorptions of nitrile imines was investigated computationally at the B3LYP/6-31G* level. IR spectra were analyzed in terms of calculated anharmonic vibrational spectra and were generally in very good agreement with the calculated spectra. Infrared spectra were found to reflect the structures of nitrile imines accurately. Nitrile imines with IR absorptions above 2200 cm(-1) have essentially propargylic structures, possessing a CN triple bond (typically PhCNNSiMe(3)23, PhCNNPh 29, and boryl-CNN-boryl 39). Nitrile imines with IR absorptions below ca. 2200 cm(-1) are more likely to be allenic (e.g., HCNNH 1, PhCNNH 6, HCNNPh 43, PhCNNCH(3)17, and Ph(3)C-CNN-CPh(3)34). All nitrile imines isomerize to the corresponding carbodiimides both thermally and photochemically. Monosubstituted carbodiimides isomerize thermally to the corresponding cyanamides (e.g., Ph-N═C═N-H 5 → Ph-NH-CN 8), which are therefore the thermal end products for nitrile imines of the types RCNNH and HCNNR. This tautomerization is reversible under flash vacuum thermolysis conditions. PMID:22364289

  4. Hot atoms in cosmic chemistry.

    PubMed

    Rossler, K; Jung, H J; Nebeling, B

    1984-01-01

    High energy chemical reactions and atom molecule interactions might be important for cosmic chemistry with respect to the accelerated species in solar wind, cosmic rays, colliding gas and dust clouds and secondary knock-on particles in solids. "Hot" atoms with energies ranging from a few eV to some MeV can be generated via nuclear reactions and consequent recoil processes. The chemical fate of the radioactive atoms can be followed by radiochemical methods (radio GC or HPLC). Hot atom chemistry may serve for laboratory simulation of the reactions of energetic species with gaseous or solid interstellar matter. Due to the effective measurement of 10(8)-10(10) atoms only it covers a low to medium dose regime and may add to the studies of ion implantation which due to the optical methods applied are necessarily in the high dose regime. Experimental results are given for the systems: C/H2O (gas), C/H2O (solid, 77 K), N/CH4 (solid, 77K) and C/NH3 (solid, 77 K). Nuclear reactions used for the generation of 2 to 3 MeV atoms are: N(p,alpha) 11C, 16O(p,alpha pn) 11C and 12C(d,n) 13N with 8 to 45 MeV protons or deuterons from a cyclotron. Typical reactions products are: CO, CO2, CH4, CH2O, CH3OH, HCOOH, NH3, CH3NH2, cyanamide, formamidine, guanidine etc. Products of hot reactions in solids are more complex than in corresponding gaseous systems, which underlines the importance of solid state reactions for the build-up of precursors for biomolecules in space. As one of the major mechanisms for product formation, the simultaneous or fast consecutive reactions of a hot carbon with two target molecules (reaction complex) is discussed. PMID:11537799

  5. Role of aldehyde dehydrogenase in hypoxic vasodilator effects of nitrite in rats and humans

    PubMed Central

    Arif, Sayqa; Borgognone, Alessandra; Lin, Erica Lai-Sze; O'Sullivan, Aine G; Sharma, Vishal; Drury, Nigel E; Menon, Ashvini; Nightingale, Peter; Mascaro, Jorge; Bonser, Robert S; Horowitz, John D; Feelisch, Martin; Frenneaux, Michael P; Madhani, Melanie

    2015-01-01

    Background and Purpose Hypoxic conditions favour the reduction of nitrite to nitric oxide (NO) to elicit vasodilatation, but the mechanism(s) responsible for bioconversion remains ill defined. In the present study, we assess the role of aldehyde dehydrogenase 2 (ALDH2) in nitrite bioactivation under normoxia and hypoxia in the rat and human vasculature. Experimental Approach The role of ALDH2 in vascular responses to nitrite was studied using rat thoracic aorta and gluteal subcutaneous fat resistance vessels from patients with heart failure (HF; 16 patients) in vitro and by measurement of changes in forearm blood flow (FBF) during intra-arterial nitrite infusion (21 patients) in vivo. Specifically, we investigated the effects of (i) ALDH2 inhibition by cyanamide or propionaldehyde and the (ii) tolerance-independent inactivation of ALDH2 by glyceryl trinitrate (GTN) on the vasodilator activity of nitrite. In each setting, nitrite effects were measured via evaluation of the concentration–response relationship under normoxic and hypoxic conditions in the absence or presence of ALDH2 inhibitors. Key Results Both in rat aorta and human resistance vessels, dilatation to nitrite was diminished following ALDH2 inhibition, in particular under hypoxia. In humans there was a non-significant trend towards attenuation of nitrite-mediated increases in FBF. Conclusions and Implications In human and rat vascular tissue in vitro, hypoxic nitrite-mediated vasodilatation involves ALDH2. In patients with HF in vivo, the role of this enzyme in nitrite bioactivation is at the most, modest, suggesting the involvement of other more important mechanisms. PMID:25754766

  6. 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

  7. 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

  8. 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.

  9. Catalytic coal liquefaction. Final report

    SciTech Connect

    Weller, S W

    1981-01-01

    Monolith catalysts of MoO/sub 3/-CoO-Al/sub 2/O/sub 3/ were prepared and tested for coal liquefaction in a stirred autoclave. In general, the monolith catalysts were not as good as particulate catalysts prepared on Corning alumina supports. Measurement of O/sub 2/ chemisorption and BET surface area has been made on a series of Co/Mo/Al/sub 2/O/sub 3/ catalysts obtained from PETC. The catalysts were derived from Cyanamid 1442A and had been tested for coal liquefaction in batch autoclaves and continuous flow units. MoO/sub 3/-Al/sub 2/O/sub 3/ catalysts over the loading range 3.9 to 14.9 wt % MoO/sub 3/ have been studied with respect to BET surface (before and after reduction), O/sub 2/ chemisorption at -78/sup 0/C, redox behavior at 500/sup 0/C, and activity for cyclohexane dehydrogenation at 500/sup 0/C. In connection with the fate of tin catalysts during coal liquefaction, calculations have been made of the relative thermodynamic stability of SnCl/sub 2/, Sn, SnO/sub 2/, and SnS in the presence of H/sub 2/, HCl, H/sub 2/S and H/sub 2/O. Ferrous sulfate dispersed in methylnaphthalene has been shown to be reduced to ferrous sulfide under typical coal hydroliquefaction conditions (1 hour, 450/sup 0/C, 1000 psi initial p/sub H/sub 2//). This suggests that ferrous sulfide may be the common catalytic ingredient when either (a) ferrous sulfate impregnated on powdered coal, or (b) finely divided iron pyrite is used as the catalyst. Old research on impregnated ferrous sulfate, impregnated ferrous halides, and pyrite is consistent with this assumption. Eight Co/Mo/Al/sub 2/O/sub 3/ catalysts from commercial suppliers, along with SnCl/sub 2/, have been studied for the hydrotreating of 1-methylnaphthalene (1-MN) in a stirred autoclave at 450 and 500/sup 0/C.

  10. Nitric oxide as a target for the hypotensive and vasorelaxing effects induced by (Z)-ethyl 12-nitrooxy-octadec-9-enoate in rats.

    PubMed

    Machado, Natália T; Maciel, Priscilla M P; Alustau, Maria C; Queiroz, Thyago M; Furtado, Fabíola F; Assis, Valéria L; Veras, Robson C; Araújo, Islânia G A; Athayde-Filho, Petrônio F; Medeiros, Isac A

    2014-10-01

    The cardiovascular effects induced by a new organic nitrate were investigated in rats. The (Z)-ethyl 12-nitrooxy-octadec-9-enoate (NCOE) was synthesized from ricinoleic acid, the major compound of the castor oil. NCOE induced significant and dose-dependent hypotension and bradycardia in normotensive rats. In rats pretreated with NCOE (60 mg/kg, i.v., once a day) for 4 consecutive days, hypotension induced by the nitrate was similar to that observed in rats that were not pretreated with the compound. The vasorelaxation induced by the compound was concentration-dependent (10(-10)-10(-3) M) in rat mesenteric artery rings, pre-contracted with phenylephrine (1 μM), with or without endothelium. Pre-incubation with PTIO (300 μM), a free radical form of NO (NO) scavenger, attenuated the NCOE vasorelaxation potency. However, in the presence of L-cysteine (3 mM), a reduced form of NO (NO-) scavenger, NCOE response was potentiated. NCOE effect was not changed in the presence of an inhibitor of cytochrome P450, proadifen (10 μM). On the other hand, the vasodilation was reduced in the presence of mitochondrial aldehyde dehydrogenase inhibitor (mtALDH), cyanamide (1 mM); soluble guanylyl cyclase inhibitor (sGC), ODQ (10 μM); and non-selective K+ channels blocker, TEA (3 mM). In addition the NCOE-induced vasorelaxation was reduced by BKCa (iberiotoxin, 100 nM) and KATP selective (glibenclamide, 10 μM) blockers, however the effect was not modified by a KV blocker (4-aminopyridine, 1 mM). Furthermore, NCOE increased NO levels in rat aortic smooth muscle cultured cells, detected by NO-sensitive probe DAF-2DA, by flow cytometry. These results together suggest that NCOE induces short-lasting hypotension and bradycardia, and promotes vasorelaxation due to NO release through the compound metabolism via mtALDH and consequent sGC, KATP and BKCa activation. Furthermore, the compound was not able to induce tolerance. PMID:24964291

  11. 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

  12. Creatine as nutritional supplementation and medicinal product.

    PubMed

    Benzi, G; Ceci, A

    2001-03-01

    function. A major point that related to the quality of creatine monohydrate products is the amount of creatine ingested in relation to the amount of contaminants present. During the industrial production of creatine monohydrate from sarcosine and cyanamide, variable amounts of contaminants (dicyandiamide, dihydrotriazines, creatinine, ions) are generated and, thus, their tolerable concentrations (ppm) must be defined and made consumers known. Furthermore, because sarcosine could originate from bovine tissues, the risk of contamination with prion of bovine spongiform encephalopathy (BSE or mad-cow disease) can t be excluded. Thus, French authorities forbade the sale of products containing creatine. Creatine, as other nutritional factors, can be used either at supplementary or therapeutic levels as a function of the dose. Supplementary doses of nutritional factors usually are of the order of the daily turnover, while therapeutic ones are three or more times higher. In a subject of 70 kg with a total creatine pool of 120 g, the daily turnover is approximately of 2 g. Thus, in healthy subjects nourished with fat-rich, carbohydrate, protein-poor diet and participating in a daily recreational sport, the oral creatine monohydrate supplementation should be of the order of the daily turnover, i.e., less than 2.5-3 g per day, bringing the gastrointestinal absorption to account. In healthy athletes submitted daily to high-intensity strength or sprint training, the maximal oral creatine monohydrate supplementation should be of the order of two times the daily turnover, i.e., less than 5-6 g per day for less than two weeks, and the creatine monohydrate supplementation should be taken under appropriate medical supervision. The oral administration of more that 6 g per day of creatine monohydrate should be considered as a therapeutic intervention and should be prescribed by physicians only in the cases of suspected or proven deficiency, or in conditions of severe stress and/or injury. The

  13. Organic matter formed from hydrolysis of metal carbides of the iron peak of cosmic elemental abundance

    NASA Astrophysics Data System (ADS)

    Cataldo, Franco

    2003-01-01

    inside the iron peak of the cosmic abundances) has been discussed as well. A survey of the hydrolytic behaviour of other carbides has been included so that all lanthanides and actinides are considered as well as carbides of the second and third groups of the periodic table of elements and highly refractory carbides such as those of Ti, Zr, Ta and W have been briefly discussed. Furthermore, the hydrolysis of mixed metal carbides and nitrides is discussed, which gives a mixture of extremely interesting molecules that are considered the raw materials for the formation of the molecules of life: guanidine, methyl hydrazine, formic acid, hydrogen cyanide, urea, cyanamide, methylamine and formaldehyde. The hydrolysis of metal carbides has also been discussed within the framework of other reactions that are well considered in the present day in an astrochemical context: the ion-molecule reaction, the Miller-Urey and the Sagan-Kaare synthesis as well as the catalytic Fischer-Tropsch synthesis and the radiation-driven Fischer-Tropsch synthesis.

  14. Is there a rationale for the use of creatine either as nutritional supplementation or drug administration in humans participating in a sport?

    PubMed

    Benzi, G

    2000-03-01

    from sarcosine and cyanamide, variable amounts of contaminants (dicyandiamide, dihydrotriazines, creatinine, ions) are generated and, thus, their tolerable concentrations (ppm) must be defined by specific toxicological researches. Creatine, as the nutritional factors, can be used either at supplementary or therapeutic levels as a function of the dose. Supplementary doses of nutritional factors usually are of the order of the daily turnover, while therapeutic ones are three or more times higher. In a subject with a body weight of 70 kg with a total creatine pool of 120 g, the daily turnover is approximately 2 g. Thus, in healthy subjects nourished with a fat-rich, carbohydrate-, protein-poor diet and participating in a daily recreational sport, the oral creatine supplementation should be on the order of the daily turnover, i.e. less than 2.5-3 g per day, bringing the gastrointestinal absorption to account. In healthy athletes submitted daily to high-intensity strength- or sprint-training, the maximal oral creatine supplementation should be on the order of two times the daily turnover, i.e. less than 5-6 g per day for less than 2 weeks, and the creatine supplementation should be taken under appropriate medical supervision. The oral administration of more than 6 g per day of creatine should be considered as a therapeutic intervention because the dosage is more than three times higher than the creatine daily turnover and more than six times higher than the creatine daily allowance. In this case, creatine administration should be prescribed by physicians only in the cases of suspected or proven deficiency, or in conditions of severe stress and/or injury. 2000 Academic Press@p$hr PMID:10675277

  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