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  1. Radioprotective properties of certain nitrogenous compounds heterocyclic on the serum proteins of irradiated mice; Proprietes radioprotectrices de certains heterocycles azotes sur les proteines seriques de souris irradiees

    Pierotti, T; Roushdy, H; Polverelli, M; Mazza, M [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    animaux. Chez les animaux irradies et proteges par les heterocycles azotes, des le quatrieme jour apres l'irradiation la restauration s'amorce et au bout de dix jours, on retrouve les concentrations normales pour chaque fraction proteinique. Le benzimidazole apparait comme un meilleur radioprotecteur que l'imidazole. (auteurs)

  2. Radioprotective properties of some heterocyclic nitrogenous compounds against spectral modifications in hemoglobin of x-irradiated mice; Proprietes radioprotectrices de certains composes heterocycliques azotes sur les modifications spectrales de l'hemoglobine de souris irradiee

    Roushdy, H; Pierotti, T; Polverelli, M [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    Imidazole and benzimidazole are known for their radioprotective action. In this work, authors have studied the radioprotective action of these compounds on visible and ultra-violet hemoglobin absorption spectra obtained from mice after in vivo X-irradiation. Results compared to those obtained with cysteamine show: 1- a possible pharmacological action of the heterocyclic nitrogenous compounds on the {alpha} and {beta} bands (540 and 580 m{mu}). 2 - a significative variation of the ratio of the optical densities (580/540) after irradiation with hemoglobin of non and radio-protected mice. However, following a real drop of absorption maxima, the twenty-fifth day after irradiation, normal optical densities of each band are found again. A physico-chemical study would be necessary to understand the hemoglobin transformation after irradiation and perhaps, its possible radioprotection. (authors) [French] Les proprietes radioprotectrices de l'imidazole et du benzimidazole etant deja connues, les auteurs ont etudie l'action de ces produits sur les spectres d'absorption de l'hemoglobine dans le visible et le proche ultra-violet apres une irradiation in vivo de souris a dose letale. L'action de ces produits comparee a celle de la cysteamine utilisee dans les memes conditions a permis de constater: 1- l'action pharmacologique probable des heterocycles azotes sur les bandes {alpha} et {beta} situees a 540 et 580 m{mu}; 2 - qu'avec et sans radioprotecteurs, les modifications spectrales se traduisaient par des variations du rapport d'intensite d'absorption existant entre les bandes a 540 et 580 m{mu}. Toutefois, apres une chute des maxima d'absorption, ceux-ci retournent aux valeurs normales le vingt-cinquieme jour apres irradiation. Une etude physicochimique complementaire de l'hemoglobine permettrait de definir la nature exacte du changement apres irradiation et peut-etre son eventuelle radioprotection. (auteurs)

  3. Radioprotective properties of some heterocyclic nitrogenous compounds against changes in hemoglobin concentration and hematocrit value in x-irradiated mice; Proprietes radioprotectrices de certains composes heterocycliques azotes sur les variations du taux d'hemoglobine et de la valeur hematocrite chez la souris irradiee

    Rousdhy, H; Pierotti, T; Polverelli, M [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    Radioprotective properties of imidazole and benzimidazole have been proved in previous works. In this study, authors try to demonstrate radioprotective action of these compounds in comparison with cysteamine upon the hematopoietic system after lethal X-irradiation. Results show: no drastic variations of hematologic constants (hemoglobin concentration and hematocrit value) after intraperitoneal injection of radioprotective compounds apart certain apparent reactions with the heterocyclic compounds; the better radioprotective action of benzimidazole. Twenty five days after irradiation, hemoglobin concentration and hematocrit of radio protected mice return to normal values. (author) [French] Les proprietes radioprotectrices de l'imidazole et du benzimidazole ayant ete demontrees dans de precedents travaux, les auteurs se sont attaches a etudier l'action de ces produits sur le systeme hematopofetique en comparaison avec celle de la cysteamine, apres une irradiation a dose letale. A l'aide des criteres choisis, les resultats demontrent: qu'en dehors de certaines reactions apparentes, succedant a l'injection intraperitoneale des heterocycles azotes, les constantes hematologiques (taux d'hemoglobine et valeur hematocrite) ne sont que legerement modifiees; la superiorite du benzimidazole sur les autres produits utilises. Enfin, le vingt-cinquieme jour apres irradiation, les souris protegees par les heterocycles azotes ont un taux d'hemoglobine et une valeur hematocrite tout a fait normaux. (auteur)

  4. Les teneurs en carbone, azote et phosphore du sol sur l'occurrence ...

    Les teneurs en carbone, azote et phosphore du sol sur l'occurrence de Lippia multiflora M. (théier de savane) et la composition chimique de son huile essentielle extraite des feuilles au Nord-Ouest de la Côte d'Ivoire.

  5. Influence de l\\'addition d\\'inhibiteurs azotés sur le comportement ...

    Influence de l\\'addition d\\'inhibiteurs azotés sur le comportement électrochimique et métallurgique de fontes au chrome-nickel (pompes d\\'extraction) en milieu ... en évidence l\\'existence d\\'un film très mince à la surface de la fonte Fa et d\\'une couche épaisse et poreuse de produits de corrosion à la surface de la fonte Fb.

  6. On the radioprotective properties of heterocyclic nitrogenous compounds; Etude des proprietes radioprotectrices de composes heterocycliques azotes

    Rinaldi, R; Bernard, Y [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1964-07-01

    Continuing their study of the possible radioprotective properties of heterocyclic nitrogenous compounds, the authors study certain derivatives of imidazole and other compounds of similar structure. The results obtained showed: 1 - that the derivatives resulting from the presence in the imidazole ring of the mercapto, methyl, carbonyl, or benzyl groups are inactive: these substitutions appear to destroy the significant radioprotective activity of the imidazole, 2 - that benzimidazole, on the contrary, seems to possess highly interesting properties. The percentage of survivals obtained with mice treated with benzimidazole and exposed to lethal irradiation has encouraged the authors to undertake careful study of this substance, with a view to define optimum activity conditions, and to determine the mechanism responsible for its radioprotective action. Further on and so as to of clarify certain points that might give useful data concerning the mechanisms of action of radioprotective chemicals, in respect of each of the products the authors have studied: a - the action of these bodies on the internal temperature of mice, b - their radioprotective activity in vitro, in a solution of irradiated hemin. (authors) [French] Les proprietes radioprotectrices de l'imidazole ayant ete mises en evidence dans un precedent travail, les auteurs poursuivent leur experimentation sur certains derives de ce noyau ainsi que des composes de structure voisine. Leurs resultats montrent: 1 - que les composes obtenus par substitution d'un groupement mercapto, methyle, carbonyle ou benzyle, a un hydrogene du noyau imidazole sont inactifs, 2 - que le benzimidazole presente par contre des proprietes interessantes. Pour ce dernier compose le pourcentage de survie pouvant atteindre 90 pour cent les auteurs ont determine les conditions optimales de son activite radioprotectrice; de plus, dans le but d'obtenir des renseignements susceptibles de preciser le mecanisme d'action de la radioprotection

  7. Influence d'un apport fractionné en potassium et en azote sur la ...

    SARAH

    31 oct. 2015 ... Influence of a fractional contribution in potassium and nitrogen on the ... dependence for this fruit-vegetable in view of its high demand by consumers. ... Journal of Applied Biosciences 94:8789 – 8800 ... fertilité des sols et de minimiser les impacts sur .... une répétition. ...... Effects of different levels of urea on.

  8. Effet de la nutrition minérale azotée sur le gain en biomasse de l'if du canada et sur le contenu en taxanes

    Jollez, Pierre-Antoine

    2008-01-01

    Dans le cadre d'un vaste programme de domestication de l'if du Canada (Taxus canadensis Marsh.) à des fins de production de taxanes, de jeunes plants en première, deuxième ou troisième années de culture en contenants ont été soumis à différentes sources d'azote (nitrate d'ammonium, nitrate de calcium, nitrate de sodium, sulfate d'ammonium et urée), appliquées à différentes doses, et à divers pH du substrat pour étudier leur influence sur la croissance des plants, sur la teneur en éléments min...

  9. Effet de pratiques de fertilisation azotée sur la sensibilité d’une culture de tomate à l’oïdium et la pourriture grise en conditions de production sous serre.

    Ozayou, Saddik

    2011-01-01

    L’azote est le principal élément nutritif utilisé pour le contrôle des maladies aériennes sous abris. Dans ce stage, nous avons étudié l’effet de trois régimes de fertilisation azotée (4 mmoles/L, 8 mmoles/L et 16 mmoles/L) sur la physiologie de la plante et la sensibilité de la tomate à l’Oidium neolycopersici et à Botrytis cinerea en conditions de production sous serre. Pour ce faire, nous avons inoculé différents organes aériens des plantes dans la serre ou au laboratoire de l’INRA d’Alény...

  10. A Nitrogen-16 Power Channel in the Melusine Cooling Circuit; Chaine de puissance azote 16 sur le circuit de refrigeration de melusine

    Tiberghien, R [Commissariat a l' Energie Atomique. Centre d' Etudes Nucleaires, 38 - Grenoble (France)

    1962-07-01

    A power channel, which is to be used on Melusine, the 2 MW pool-type reactor built at Grenoble Nuclear Center, is described. It will be used for measuring of {sup 16}N activity of water after passage through the reactor core. The experimental system as well as the measuring instruments are described. Solutions to problems likely to arise are given. The experimental results show that this power measurement is free from neutron flux local deformations, from control rods position, and from experiments. The power indicated is to {+-}2% the same as the thermodynamic power. Since May 1962, this power channel is used as a reference for the operation of the reactor. It is also provided for on the Siloe 10 MW reactor. (author) [French] L'objet de ce rapport est la description d'une nouvelle chaine de puissance pour la pile piscine 'Melusine' de 2 MW du Centre d'etudes Nucleaires de Grenoble. Il s'agit de la mesure de l'activite en azote 16 de l'eau apres son passage dans le coeur du reacteur. Le dispositif experimental ainsi que les appareils de mesure y sont decrits. Les reponses aux differents problemes poses sont donnees. Les resultats experimentaux montrent que cette mesure de puissance est independante des deformations locales de flux de neutrons, de la position des barres de controle et des manipulations. La puissance indiquee par cette chaine est a 2 % pres identique a la puissance thermodynamique. Depuis mai 1962, elle est utilisee comme reference pour le pilotage de la pile. Elle est aussi prevue sur la pile 'Siloe' de 10 MW. (auteur)

  11. Action de I'AlA sur la teneur en azote total et protéinique des graines de céréales cultivées à different niveau de la capacité capillaire en eau

    Wiesław Nowakowski

    2015-06-01

    Full Text Available L'action de I'AIA sur la teneur en azote total et en azote protéinique des graines du Triticum vulgare, d'Hordeum vulgare et d'Avena sativa cultivés a 30%, 60% et 90% de la capacité capillaire en eau du sable a tété étudiée au cours de trois ans (1969, 1970, 1971. La teneur en g-protéines totales liée au rendement des graines de céréales examinees a été plus élevée dans les conditions de sécheresse (30% de la capacite capillaire en eau à la suite d'un traitement auxinique. La teneur (% en azote total et proteinique ne semble pas etre tellement modifiee dans les graines de cereales à la suite d'un traitement auxinique.

  12. Compétition pour l'azote inorganique entre le pelagos et le benthos dans un écosystème côtier oligotrophe. Effets sur la dynamique de l'écosystème.

    Lepoint, Gilles

    2001-01-01

    Résumé de la thèse intitulée : Compétition pour l’azote inorganique entre le benthos et le pelagos d’un milieu côtier oligotrophe. Effets sur la dynamique de l’écosystème. Dissertation présentée le 9 mai 2001 par Gilles Lepoint en vue de l’obtention du grade de Docteur en Sciences de l’Université de Liège. Dans la Baie de la Revellata (Calvi, Corse, France), comme dans de nombreux sites côtiers méditerranéens, les biocénoses benthiques sont très développées et productives, malgré le c...

  13. Influence of oxygen, nitrogen and carbon on the lattice parameter of uranium mono-carbide; Influence de l'oxygene, de l'azote et du carbone sur le parametre reticulaire du monocarbure d'uranium

    Magnier, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1966-04-15

    The author studies the influence of oxygen and nitrogen contents on the lattice parameter of U(C,O,N) solid solutions around UC composition. The whole data conducts to a determination of the solubility of oxygen in UC: a U(C(1-x)O(x)) solid solution exist if x if smaller than 0.37. The author studies also the influence of carbon content on the lattice parameter of U-UC solid solutions around UC. This study conducts to the determination of the solubility of U in UC at the different temperatures. Consequences upon uranium-carbon diagram are envisaged. (author) [French] L'auteur etudie quantitativement l'influence de l'oxygene et de l'azote sur le parametre reticulaire des solutions solides U(C,O,N) proches de UC. Cette etude permet la determination de la solubilite de l'oxygene dans UC: on montre l'existence d'une solution solide U(C(1-x)O(x)) lorsque x est compris entre 0 et 0,37. Par ailleurs l'auteur etudie l'influence de la teneur en carbone sur le parametre des solutions solides U-UC proches de UC. Cette etude permet la determination de la solubilite de l'uranium dans UC aux differentes temperatures. On envisage enfin les modifications apportees par cette etude au diagramme uranium-carbone. (auteur)

  14. Rentabilité économique du fractionnement des engrais azotés en ...

    SARAH

    29 mai 2013 ... RESUME. Objectifs : Les engrais se minéralisent pendant toute la saison de végétation et la disponibilité de l'azote ne coïncide pas toujours avec le cycle de croissance des cultures. Ainsi, le fractionnement de l'azote et son application sur deux variétés améliorées de maïs, Unilu et PAN 53, a été explorée ...

  15. Etude paramétrique des effets de la stratification de la flamme sur les émissions d'oxydes d'azote (première partie Parametric Study of Statification Effects on Nitric Oxyde Emissions from Flam (Part One

    De Soete G.

    2006-11-01

    Full Text Available On a étudié les effets de la stratification de flammes de prémélange laminaires, stationnaires et non stationnaires, sur les émissions d'oxydes d'azote formés par le mécanisme thermique et par le mécanisme du fuel-NO. Deux modalités de stratification ont été considérées, l'une juxtaposant sur le même plan les zones de combustion primaires correspond aux fractions individuelles du mélange stratifié (stratification en juxtaposition, l'autre disposant ces zones de combustion primaires sur des plans successifs (stratification en succession. Les émissions d'oxydes d'azote mesurées sur les flammes stratifiées ont été comparées à celles provenant de flammes non stratifiées de même composition globale et brûlant dans des conditions identiques. L'étude montre qu'il y a lieu de distinguer deux types d'effets de stratification. II existe un effet primaire -qui est la simple conséquence du morcellement de la flamme en un certain nombre de zones de combustion primaires (caractérisées par des compositions différentes et qui se traduit par l'additivité des émissions individuelles provenant des fractions respectives du mélange. L'effet total de la stratification se réduit à ce seul effet primaire au cas où les vitesses de formation des oxydes d'azote deviennent nulles après re-mélange des produits de combustion provenant des différentes fractions du mélange stratifié. Il en est ainsi par exemple dans le cas des flammes non stationnaires stratifiées en succession ; il en résulte alors soit une augmentation soit une diminution des émissions d'oxydes d'azote par rapport à celles des flammes non stratifiées, suivant la valeur de la richesse globale et du degré de stratification. Des effets secondaires de stratification se manifestent chaque fois que des produits de combustion, provenant d'une zone de combustion primaire donnée, sont introduits totalement ou partiellement dans un autre front de flamme créé par la

  16. Le carbone et l'azote dans les différentes fractions granulométriques ...

    SARAH

    21 janv. 2014 ... permis de suivre l'évolution du carbone organique et de l'azote total du sol. Les résultats ... impact sur le flux de CO2 à partir de la surface du sol. (Creamer et al. ...... estimates of CO2 emissions from soil in response to global ...

  17. Present Status of Nitrogen Fixation by Reactor Radiation; Etat Actuel des Recherches sur l'oxydation directe de l'azote sous irradiation dans des reacteurs; Sovremennoe sostoyani opytov po okisleniyu azota izlucheniem iz reaktorov; Estado actual de las investigaciones sobre fijacion del nitrogeno por irradiacion en reactores

    Harteck, P; Dondes, S [Rensselaer Polytechnic Institute, Troy, NY (United States)

    1960-07-15

    'oxydation directe de l'azote sous irradiation, entreprises depuis plusieurs annees par le Rensselaer Polytechnic Institute et le Brookhaven National Laboratory, utilisent directement les particules de recul de fission comme rayonnements ionisants, au moyen de la dispersion d'uranium-235 dans des fibres de verre de cinq microns de diametre environ. Les auteurs ont determine les effets de la temperature, de la pression et du rapport azote/oxygene sur la valeur de G pour l'oxydation de l'azote et ont publie le compte rendu de leurs travaux. Ils en donnent un bref apercu. Les recherches en question ont ete effectuees avec des systemes statiques; plus recemment des systemes statiques et des systemes a circulation ont ete utilises a la fois. Avec les systemes statiques, les auteurs se sont surtout attaches a etudier l'effet de l'intensite des rayonnements, notamment sur la cinetique d'equilibre sous irradiation. Ils ont constate que dans des melanges ou le rapport azote/oxygene est de 4 a 1 et de 2 a 1 N0{sub 2} et N{sub 2}0 se forment jusqu'a epuisement de tout l'oxygene present. Un systeme a circulation continue (cycling) fonctionne maintenant dans une boucle a l'interieur du reacteur de Brookhaven. Les auteurs fournissent sur les effets de la temperature, de la pression, du rapport azote/oxygene et de l'intensite des rayonnements des donnees que l'on pourra utiliser pour etablir un projet de reacteur de chimie nucleaire. Le systeme actuel fonctionne sous 10 atmospheres et a 150{sup o}C. La temperature est fonction de l'energie de fission liberee dans les fibres de verre et de la resistance thermique du circuit. Une autre boucle, qui doit fonctionner sous 50 - 75 atmospheres et a 600{sup o} C, est en construction. Il est possible, grace a ces boucles, d'etudier les caracteristiques d'un systeme continu, y compris le comportement des produits de fission liberes dans le courant, gazeux. Les auteurs distinguent trois stades dans la cinetique complexe de l'oxydation de l'azote: reactions

  18. Les oxydes d'azote dans l'environnement Nitrogen Oxides in the Environment

    Oppeneau J. C.

    2006-11-01

    Full Text Available Le présent article expose les concentrations en oxydes d'azote rencontrées dans l'environnement et fait la part des origines naturelles et anthropogéniques. II présente une des manifestations les plus connues des interactions entre les oxydes d'azote, les molécules organiques, la vapeur d'eau et le rayonnement solaire le brouillard photochimique. Un certain nombre de données sur les effets d'oxydes d'azote sur l'homme et le milieu sont cités et il est mentionné que de nombreuses recherches sont à effectuer pour préciser les connaissances actuelles. Enfin, les réglementations présentes et futures sont décrites. This article describes concentrations of nitrogen oxides found in the environment and explains their natural and anthropogenic origins. It describes one of the best known examples of interactions between nitrogen oxides, organic molecules, water vaporand solorradiation, i. e. photochemical smog. Various data are brought outconcerning the effects of nitrogen oxides on man and the environment, and mention is mode of the many research projects being carried out ta specify current knowledge. Present and future regulations are also described.

  19. Handbook of heterocyclic chemistry

    Katritzky, Alan R

    2010-01-01

    ... Heterocyclic Chemistry I (1984) Comprehensive Heterocyclic Chemistry II (1996) Comprehensive Heterocyclic Chemistry III (2008) Comprehensive Organic Functional Group Transformations I (1995) Compreh...

  20. Lixiviation du potassium sous culture de pomme de terre irriguée en sol sableux : impact des engrais azotés

    Chaouechi, Ameni

    2014-01-01

    Au Québec, la pomme de terre est cultivée sur des sols sableux favorisant les pertes par lixiviation de l’azote et du potassium. Selon le principe de réactions d’échanges cationiques, on a supposé que les doses et les sources d'azote puissent avoir un impact sur la lixiviation du potassium. Ainsi, une expérience a été menée, pendant trois années, dans un champ de pomme. Le dispositif expérimental est un bloc complet aléatoire de quatre répétitions constitué de 10 traitements qui sont un facto...

  1. Émissions azotées au champ et performances des machines lors de l'épandage de boues issues du traitement des eaux usées

    Pradel, M.; Pacaud, T.; Cariolle, M.

    2011-01-01

    / Ce document est un rapport de synthèse des travaux réalisés dans le cadre du projet Ecodefi sur l'estimation des émissions azotées lors de l'épandage de boues issues du traitement des eaux usées en lien avec les performances technologiques des machines utilisées à cet effet.

  2. Automatic filling of liquid nitrogen traps auxiliary safety devices of a pumping unit; Alimentation automatique des pieges a azote liquide securites annexes d'un groupe de pompage

    Chatel, S [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1969-07-01

    The liquid nitrogen traps in our laboratories are generally filled at fixed time intervals, the supply being cut when the liquid flowing through the overflow pipe acts on a lever to which is fixed a small cup fitted with a hole which allows the water of condensation to escape. This system is reliable. After a certain time however, the escape hole blocks up, water accumulates and the lever arm no longer works properly. Furthermore the duration of any cuts in the current, is added to the fixed time intervals, and in this case there can be a lack of liquid nitrogen for several hours after the current has been restored. The device described here avoids these problems. A stainless steel tube containing a copper wire passes into the trap and is immersed in the nitrogen which boils at its tip. A mercury manometer with concentric reservoirs, or an oil manometer, acting on two micro switches through a floater, records the pressure corresponding to the difference in level and controls the filling operation. If there is a lack of nitrogen, a valve can be closed by means of a falling weight, or a diffusion pump can be cut off; one time switch and at least two relays are required. One single relay can be used to control, the supply of several similar traps placed in series. [French] Dans nos laboratoires, les pieges a azote liquide sont generalement remplis a intervalles fixes jusqu'a ce que le trop-plein d'azote actionne une bascule dont le recipient presente un petit trou par ou s'en va l'eau de condensation. Ce systeme est sur. A la longue, pourtant, le trou d'ecoulement se bouche, l'eau s'accumule et la bascule cesse de fonctionner. De plus, la duree des pannes de courant s'ajoute aux 'intervalles fixes' de sorte que l'azote peut manquer plusieurs heures apres le retour du courant. Le dispositif suivant evite ces ennuis. Un tube d'acier inoxydable contenant un fil de cuivre penetre dans le piege et plonge dans l'azote qui bout a son extremite. Un manometre a mercure a cuves

  3. Reaction of uranium and plutonium carbides with nitrogen; Reaction avec l'azote des carbures d'uranium et de plutonium

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

    1966-03-01

    Uranium and plutonium carbides react with nitrogen during the grinding process preceding the final sintering. The reaction occurs even in argon atmospheres containing a few percent of residual nitrogen. The resulting contamination is responsible for the appearance of an equivalent quantity of higher carbide in the sintered products; nitrogen remains quantitatively in the monocarbide phase. UC can be transformed completely into nitride under a nitrogen pressure, at a temperature as low as 400 C. The reaction is more sluggish with PuC. The following reactions take places: UC + 0,8 N{sub 2} {yields}> UN{sub 1.60} + C and PuC + 0,5 N{sub 2} {yields} PuN + C. (authors) [French] Les carbures d'uranium et de plutonium reagissent avec l'azote au cours du broyage qui precede le frittage final. Cette reaction est sensible meme sous des atmospheres d'argon ne contenant que quelques pour cent d'azote. Cette contamination se traduit sur les produits frittes par l'apparition d'une quantite equivalente de carbure superieur, l'azote restant fixe quantitativement dans la phase monocarbure. On peut transformer entierement UC en nitrure par action de l'azote sous pression des 400 C. La reaction est plus difficile avec PuC. Les reactions sont les suivantes: UC + 0,8 N{sub 2} {yields} UN{sub 1.60} + C et PuC + 0,5 N{sub 2} {yields} PuN + C.

  4. Principle of a liquid nitrogen irradiation device and its realization for use in a swimming-pool type reactor; Principe d'un dispositif d'irradiation a azote liquide et sa realisation pour utilisation dans une pile piscine

    Bochirol, L; Doulat, J; Weil, L [Commissariat a l' Energie Atomique, Grenoble (France).Centre d' Etudes Nucleaires

    1961-07-01

    The problem of pile irradiation of samples immersed in liquid nitrogen has been solved with total elimination of explosion hazards and high reliability (no moving parts). The principle of the device is that of a double bath: one of high purity nitrogen cools the samples at the level of the core; a second of commercial nitrogen is located above the first one, outside the high radiation field, and works as a continuous condenser for the pure nitrogen, the flow-back of which is provided simply by gravity. The apparatus described in detail here has been designed for a swimming-pool pile. It was so designed as to provide absolute protection against radiations and to allow the irradiated samples to be easily removed in the cold condition. This apparatus has been in operation for several months. In a fast flux greater than 10{sup 13} neutrons/cm{sup 2}.s and a {gamma}-flux of the order of 10{sup 8} roentgens/h, the consumption of liquid nitrogen is of the order of 100 liters a day. (author) [French] On a resolu le probleme de l'irradiation en pile d'echantillons immerges dans l'azote liquide en construisant un appareil d'un fonctionnement sur (aucune partie n'est mobile) qui elimine completement les dangers d'explosion. Le principe de l'appareil est celui d'un double bain: l'un, d'azote pur, refroidit les echantillons au niveau du coeur du reacteur; l'autre, d'azote commercial, est situe au-dessus du premier, hors du champ de rayonnement intense, et sert de condenseur continu pour l'azote pur. Ce dernier ainsi reliquefie regagne son bain par simple gravite. L'appareil decrit en detail ici, est concu pour une pile piscine. Il a ete etudie de facon a ne creer aucune fuite de rayonnement et a permettre la recuperation aisee des echantillons irradies sans rechauffage de ceux-ci. Cet appareil est en fonctionnement depuis plusieurs mois. Dans un flux rapide superieur a 10{sup 13} neutrons/cm{sup 2}.s et un flux {gamma} de l'ordre de 10{sup 8} roentgens/h, la consommation d'azote

  5. MODELISATION DE LA CINETIQUE CHIMIQUE DANS LA REDUCTION DES OXYDES D4AZOTE PAR DECHARGE COURONNE.

    MEDJAHDI, Sarah ines

    2015-01-01

    CE TRAVAIL DE recherche rentre dans le cadre général de modélisation de la réduction des oxydes d'azote . l'utilisation des réacteurs a plasma froid non-thermique généré par des décharges couronnes est actuellement l'une des techniques les puis promettre .ses pour la destruction des oxydes d'azote .en effet , le traitement des gaz pollués par les décharges couronnes est notamment rendu possible par la multiplication des décharges Électriques .

  6. Controle optique de qubits lies a des centres isoelectroniques d'azote dans le GaAs

    Ethier-Majcher, Gabriel

    manipuler des spins electroniques. Les excitons et excitons charges lies aux paires d'azote sont etudies par la photoluminescence resolue spatialement. Le controle des qubits excitoniques est realisee a l'aide d'impulsions laser resonantes avec un etat excitonique et l'etat du qubit est lu par sa fluorescence en resonance. Une experience de rotations de Rabi est realisee pour demontrer un controle sur la population du qubit. Cette experience permet d'extraire un moment dipolaire moyen de 27 D pour l'exciton.

  7. Dynamique de la teneur en carbone et en azote des sols dans les ...

    SARAH

    30 nov. 2014 ... INTRODUCTION. L'étude de la dynamique de carbone et de l'azote dans le ... climatique et l'autre de dimension locale, la fertilité des sols. ... situe à la limite méridionale du domaine sahélien, le ..... Soils and global change.

  8. Contribution to the isotopic analysis of nitrogen using optical spectrometry; Contribution a l'analyse isotopique de l'azote par spectrometrie optique

    Leicknam, J P [Commissariat a l' Energie Atomique, 91 - Saclay (France). Centre d' Etudes Nucleaires

    1968-07-01

    15 (abondances isotopiques inferieures a 2 pour cent), les methodes proposees jusqu'alors ne donnaient pas rapidement des resultats suffisamment precis. Cette analyse isotopique ne necessite qu'un spectrometre de moyenne resolution; on peut meme, comme nous l'avons fait, utiliser un spectrographe en substituant a la plaque photographique une fente de sortie, suivie d'un photomultiplicateur; cette transformation est tres simple a realiser et les signaux provenant du detecteur peuvent alors etre envoyes sur un enregistreur. Dans ces conditions la duree d'une determination ne demande que de trois a dix minutes, suivant la precision desiree. Les sources de lumiere sont constituees par des lampes a decharge sans electrode, excitees par haute frequence; les conditions de remplissage sont telles que l'on peut preparer des lampes en quelques minutes, les impuretes etant suffisamment eliminees pour ne pas perturber les mesures. Le choix du couple de bandes d'analyse tient compte de la position relative des bandes isotopiques et de la presence eventuelle de traces de ces impuretes: parmi les transitions du systeme C({sup 3}{pi}{sub u}) <-> B({sup 3}{pi}{sub g}), la transition 2 {yields} 0 presente la disposition la plus favorable pour effectuer ce dosage isotopique. La methode est appliquee a des echantillons de diverses provenances (sels ammoniacaux, engrais et plantes): les teneurs isotopiques sont determinees a 3 pour cent pres au voisinage de l'abondance naturelle et a 1 pour cent pres lorsque l'echantillon contient environ 1.5 atomes d'azote 15 pour 100 atomes d'azote 14. La precision est donc largement suffisante pour la plupart des etudes biologiques utilisant, l'atome 15 comme traceur. (auteur)

  9. Devenir De l'azote de L'engrais enrichi au n applique au tournesol ...

    L'utilisation de I' azote de I' engrais par la culture de toumesol a ete appreciee par Ia determination du coefficient d'utilisation apparent (CUA) estime par Ia methode de difference et du coefficient d'utilisation reel (CUR) estime par Ia methode isotopique. 80 kg N ha-1 a 4.87% d'atomes en exces de 15N ont ete appliques au ...

  10. La copla de moral sefardí Azote de impíos

    Romero, Elena

    2010-06-01

    Full Text Available Three versions of the Sephardic “Copla de moral” Azote de Impios (‘Scourge of the Wicked’ are analyzed in this article. They were all printed in the nineteenth century, in Constantinople (1858 (version A, in Leipzig (1858 (version B and in Jerusalem (1894 (version C. The Version B was included in the German Nach Jerusalem! by Ludwig Aug. Frankl is of interest as it was written with Latin letters according to a special system that reflects the sounds of the original Judeo-Spanish.En el presente artículo se lleva a cabo la edición y estudio de las tres versiones conocidas de la copla de moral sefardí titulada Azote de impíos, impresas las dos primeras en 1858 en Constantinopla (versión A y Leipzig (versión B, respectivamente, y la tercera en Jerusalén en 1894 (versión C. La versión B, inserta en el libro alemán Nach Jerusalem! de Ludwig Aug. Frankl, presenta la particularidad de estar escrita en caracteres latinos siguiendo un muy especial sistema para plasmar los sonidos del judeoespañol.

  11. Nitrous Oxide from Combustion and Industry: Chemistry, Emissions and Control Protoxyde d'azote provenant de la combustion et de l'industrie : chimie, émissions et techniques de réduction

    De Soete G.

    2006-11-01

    'industrie chimique, d'autre part il s'interroge sur les technologies possibles de destruction de N2O dans les cas où sa teneur dans les fumées ou autres effluves industriels pose des problèmes. Comme les émissions, aussi bien que les moyens de les abattre, sont fortement tributaires des mécanismes chimiques responsables de la production et de la destruction du N2O, une introduction substantielle sur la cinétique homogène et hétérogène de sa formation/réduction, telle qu'elle apparaît dans un contexte de combustion, est fournie, permettant au lecteur de comprendre le pourquoi de ces émissions et le comment des technologies d'abattement suggérées. Dans une première section de l'introduction, on rappelle brièvement la chimie du N2O en phase gazeuse et ses relations avec la chimie du monoxyde d'azote NO (fig. 1 ; l'effet de la température sur la production nette de N2O est accentué, puisqu'elle expliquera en grande partie les émissions relativement élevées de la combustion à basse température, telle qu'elle est mise en oeuvre dans les lits fluidisés (fig. 2. On mentionne pour finir les réactions du système rédox SO2/NO (fig. 3, responsable de la formation artificiellede N2O dans les échantillons de fumées stockés. La deuxième section de l'introduction traite de la chimie hétérogène du protoxyde d'azote, dont la compréhension est actuellement encore relativement fragmentaire. Parmi les mécanismes hétérogènes non catalytiques, figurent principalement : la réduction de N2O sur le carbone constitutif du charbon et du coke, la formation de N2O à partir de l'azote constitutif de ces derniers et la production de N2O par des réactions entre carbone, NO et sulfates. Les deux premiers mécanismes sont traités en parallèle avec ceux, similaires, qui opèrent sur le NO, auxquels ils sont intimement liés (voir tableau 1 et réactions S1 à S8 dans le texte. La réduction de N20 sur carbone constitutif ne produit que peu de N2O, au moins en absence d

  12. Azomesogens with a heterocyclic moiety

    Unknown

    Azomesogens with a heterocyclic moiety. †. JAYRANG S DAVE and MEERA MENON*. Department of Applied Chemistry, Faculty of Technology and Engineering, MS University of Baroda,. Baroda 390 001, India. Abstract. Azobenzene derivatives were among the first ten liquid crystalline compounds. But there have been.

  13. Teneurs azotée et minérale des espèces fourragères dominantes et ...

    SARAH

    31 mars 2016 ... sous abri, bien aérés, sans contact direct avec le soleil. Ils doivent être compacts et durs. RESULTATS. Teneur en Matières Azotées : Les résultats des analyses de la teneur en matières azotées des espèces. Bulbostylis laniceps,. Hyparrhenia wombaliensisi, Trachypogon spicatus et Ctenium newtonii.

  14. L'azote ammoniacal, un toxique potentiel en élevage de poissons : le cas du turbot

    PERSON-LE RUYET J.

    1998-07-01

    Full Text Available L'azote ammoniacal est un toxique potentiel en élevage de poissons ayant des effets plus ou moins sévères selon la concentration ambiante et la durée d'exposition. Dans une première partie, nous rappelons que l'AAT (somme de NH4+ et NH3 est toxique essentiellement sous sa forme NH3 . Dès qu'un poisson se trouve en présence de niveaux d'AAT anormalement élevés, il y a entrée d'AAT surtout sous forme de NH3 et diffusion dans les différents compartiments du poisson (à l'équilibre, le NH4+ est dominant. Selon les conditions d'exposition, différents états d'équilibre se succèdent entre le poisson et le milieu dès lors que ses capacités d'excrétion sont affectées. A partir d'un certain niveau de concentration d'AAT dans le sang et les tissus, le poisson n'arrive plus à réguler ses fonctions vitales, le seuil de toxicité est atteint. Nous faisons ensuite la synthèse de l'état des connaissances des effets de l'AAT sur la survie et la croissance du turbot (Psetta maxima en le comparant à d'autres espèces de poissons élevées en mer ou en eau douce. A court terme, la sensibilité du turbot à l'AAT est du même ordre de grandeur que celle de la daurade et du bar, la 96-h CL50 (concentration létale pour 50 % de la population varie dans une fourchette de 1 à 3 mg/l NH3 . Des valeurs aussi élevées ne peuvent être qu'accidentellement rencontrées, même dans les élevages à haute densité. Chez toutes les espèces marines éprouvées, le seuil de toxicité chronique est plus bas, 0,8-1 mg/l NH3 pour une durée d'exposition n'excédant pas un mois. Chez le turbot, la croissance est ralentie à 0,33 mg/l NH3 en moyenne et sensiblement aux mêmes valeurs chez le bar et la daurade. Chez ces mêmes espèces selon la duré d'exposition, il y a risque de perturbation de la croissance au-dessus de 0,11 mg/l NH3 , ce qui correspond aux pics de concentrations dans les élevages à haute densité utilisant des circuits fermés. Ces

  15. Heterocyclic Scaffolds: Centrality in Anticancer Drug Development.

    Ali, Imran; Lone, Mohammad Nadeem; Al-Othman, Zeid A; Al-Warthan, Abdulrahman; Sanagi, Mohd Marsin

    2015-01-01

    Cancer has been cursed for human beings for long time. Millions people lost their lives due to cancer. Despite of the several anticancer drugs available, cancer cannot be cured; especially at the late stages without showing any side effect. Heterocyclic compounds exhibit exciting medicinal properties including anticancer. Some market selling heterocyclic anticancer drugs include 5-flourouracil, methortrexate, doxorubicin, daunorubicin, etc. Besides, some natural products such as vinblastine and vincristine are also used as anticancer drugs. Overall, heterocyclic moeities have always been core parts in the expansion of anticancer drugs. This article describes the importance of heterocyclic nuclei in the development of anticancer drugs. Besides, the attempts have been made to discuss both naturally occurring and synthetic heterocyclic compounds as anticancer agents. In addition, some market selling anticancer heterocyclic compounds have been described. Moreover, the efforts have been made to discuss the mechanisms of actions and recent advances in heterocyclic compounds as anticancer agents. The current challenges and future prospectives of heterocyclic compounds have also been discussed. Finally, the suggestions for syntheses of effective, selective, fast and human friendly anticancer agents are discussed into the different sections.

  16. Electronic bond tuning with heterocyclic carbenes

    Falivene, Laura

    2013-01-01

    We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

  17. Nitrous Oxide Formation and Destruction by Industrial No Abatement Techniques Including Scr Emissions des protoxides d'azote par des techniques industrielles d'abattement de NO y compris le SCR

    De Soete G. G.

    2006-11-01

    'investigations systématiques concernant les émissions de N2O d'unités de combustion stationnaire d'échelle industrielle, équipées de technologies d'abatement de NO. Les études effectuées en laboratoire, présentées ici, suggèrent que des techniques d'étagement du combustible, de réduction sélective non catalytique (NCSR et catalytique (CSR du NO, doivent être considérées comme des sources potentielles d'augmentation des émissions de protoxyde d'azote. L'étude utilise un réacteur (fig. 1 permettant l'étagement de flammes laminaires C2H4/O2/Ar en deux fractions Fl et F2, respectivement caractérisées par un débit D1 et D2 et une richesse R1 et R2; Rg désigne la richesse globale des deux fractions. La fraction Fl brûle sous forme de flamme de prémélange plate sur un brûleur (B1 constitué d'une plaque en bronze fritté; la fraction F2, injecté dans une double couronne à points d'injection multiples (B2 brûle sous forme de flamme de diffusion, après mélange avec les produits de combustion de la fraction Fl. La distance (X entre les deux brûleurs B1 et B2 est variable. 1. Formation de N2O due à l'étagement du combustible Le monoxyde d'azote est introduit en prémélange avec la fraction Fl. Sa concentration après mélange avec les produits de combustion de Fl est désignée par NOin. La figure 2 donne la fraction de l'azote du NO transformée en N2O (Fn en fonction de R1 avec Rg comme paramètre. Les températures mesurées au point d'injection (Tx y correspondant sont présentées sur la figure 3. On observe (1 qu'une séquence de stratification riche - pauvre est généralement plus favorable à la formation de N2O qu'une séquence pauvre - riche (fig. 1, (2 que Fn diminue lorsque Tx augmente (fig. 4 et 5 ou lorsque la concentration de l'oxygène décroît (fig. 6. Ces tendances, généralement observées dans le cas de la combustion en phase gazeuse, s'expliquent qualitativement par les réactions principales de formation et de destruction du N2O

  18. Intérêt économique de l'utilisation de l'azote pour la récupération assistée du pétrole Economic Interest of Using Nitrogen for Enhanced Oil Recovery

    Bolzer M.

    2006-11-01

    Full Text Available Au cours des dix dernières années, l'injection de gaz miscibles dans les puits de pétrole a connu un nouvel essor avec l'intérêt suscité par l'emploi de gaz carbonique principalement aux Etats-Unis. Mais d'autres gaz non hydrocarbonés sont susceptibles d'être utilisés pour la récupération assistée du pétrole. C'est ainsi que l'azote ou les gaz de fumées constituent une solution de rechange éventuelle. Dans cette perspective, on peut se limiter en première analyse à l'étude économique de l'utilisation de l'azote pour des champs à terre dans des conditions Europe de l'Ouest mi-1984 avec un facteur de marche des installations de surface de 340 jours/an et une durée de vie du projet de 10 ans. Des différents résultats, il ressort que - pour des faibles demandes, chaque cas doit être l'objet d'un examen particulier; cette attitude résulte du prix de vente minimum rentable élevé d'obtention de l'azote sous forme liquide par distillation cryogénique de l'air, qui en général est compris, pour un taux de rentabilité interne de 15 %, entre 850 et 550 FF/t pour des capacités de production de 100 à 500 t/j; - pour des débits plus importants, la construction d'une unité de production d'azote gazeux sur le site même apparaît comme la solution la plus intéressante. En effet, pour des demandes comprises entre 1 500 et 5 000 t/j, on peut ainsi produire de l'azote sous 24 10·6 Pa abs à un prix de vente minimum rentable, pour un taux de rentabilité interne de 15 %, d'environ 200 FF/t, voire même 150 FF/t. In the last ten years, miscible gas flooding has taken great strides owing to the development of carbon dioxide, especially in the United States. But other non-hydrocarbon gases are likely to be used for Enhanced Oil Recovery. For example, nitrogen or flue gases appear as a possible replacement solution. With this outlook, a first analysis has been realised, limited to an economic study of using nitrogen for onshore

  19. Effets de la fertilisation azotée, de l'inoculation par Rhizobium sp. et du régime des pluies sur la production de la biomasse et la teneur en azote du pois chiche

    Lachaâl M.

    2009-01-01

    Full Text Available Effect of nitrogen fertilization, inoculation with Rhizobium sp. and precipitation on the biomass production and nitrogen content of chickpea. Water availability and soil fertility (especially soil N content are the major factors affecting chickpea yield in Mediterranean regions, characterized by low rainfall, poorly distributed and rapid mineralization of organic matter. In order to study the effect of N-fertilization and inoculation with Rhizobium on chickpea biomass production and N-content, field experiment were carried out at two stations of INRAT in northern Tunisia during two consecutive years, 2000-2001 and 2001-2002. Results showed that N-fertilization significantly increased shoot biomass and N-content while decreasing nodule mass. Inoculation with both the two Rhizobium strains resulted in nodule mass increase but the shoot N-content was not significantly affected. Regardless of the stations and treatments, rainfall decrease between the two years of the experiment significantly reduced shoot and root biomass while improving nodulation, especially at Oued Beja. However, the nodule developed under water deficit conditions was correlated with a very high decrease of the nitrogen fixed. Nevertheless, the mineral nitrogen apply in soil improved the N-content of aerial parts in the two stations, especially in waterless season.

  20. Heterocyclic anions of astrobiological interest

    Cole, Callie A.; Demarais, Nicholas J.; Bierbaum, Veronica M.; Yang, Zhibo; Snow, Theodore P.

    2013-01-01

    As more complex organic molecules are detected in the interstellar medium, the importance of heterocyclic molecules to astrobiology and the origin of life has become evident. 2-Aminothiazole and 2-aminooxazole have recently been suggested as important nucleotide precursors, highlighting azoles as potential prebiotic molecules. This study explores the gas-phase chemistry of three deprotonated azoles: oxazole, thiazole, and isothiazole. For the first time, their gas-phase acidities are experimentally determined with bracketing and H/D exchange techniques, and their reactivity is characterized with several detected interstellar neutral molecules (N 2 O, O 2 , CO, OCS, CO 2 , and SO 2 ) and other reactive species (CS 2 , CH 3 Cl, (CH 3 ) 3 CCl, and (CH 3 ) 3 CBr). Rate constants and branching fractions for these reactions are experimentally measured using a modified commercial ion trap mass spectrometer whose kinetic data are in good accord with those of a flowing afterglow apparatus reported here. Last, we have examined the fragmentation patterns of these deprotonated azoles to elucidate their destruction mechanisms in high-energy environments. All experimental data are supported and complemented by electronic structure calculations at the B3LYP/6-311++G(d,p) and MP2(full)/aug-cc-pVDZ levels of theory.

  1. Heterocyclic anions of astrobiological interest

    Cole, Callie A.; Demarais, Nicholas J.; Bierbaum, Veronica M. [Department of Chemistry and Biochemistry, 215 UCB, University of Colorado, Boulder, CO 80309 (United States); Yang, Zhibo [Department of Chemistry and Biochemistry, University of Oklahoma, Norman, OK 73019 (United States); Snow, Theodore P., E-mail: Callie.Cole@colorado.edu, E-mail: Nicholas.Demarais@colorado.edu, E-mail: Veronica.Bierbaum@colorado.edu, E-mail: Zhibo.Yang@ou.edu, E-mail: Theodore.Snow@colorado.edu [Department of Astrophysical and Planetary Sciences, 391 UCB, University of Colorado, Boulder, CO 80309 (United States)

    2013-12-20

    As more complex organic molecules are detected in the interstellar medium, the importance of heterocyclic molecules to astrobiology and the origin of life has become evident. 2-Aminothiazole and 2-aminooxazole have recently been suggested as important nucleotide precursors, highlighting azoles as potential prebiotic molecules. This study explores the gas-phase chemistry of three deprotonated azoles: oxazole, thiazole, and isothiazole. For the first time, their gas-phase acidities are experimentally determined with bracketing and H/D exchange techniques, and their reactivity is characterized with several detected interstellar neutral molecules (N{sub 2}O, O{sub 2}, CO, OCS, CO{sub 2}, and SO{sub 2}) and other reactive species (CS{sub 2}, CH{sub 3}Cl, (CH{sub 3}){sub 3}CCl, and (CH{sub 3}){sub 3}CBr). Rate constants and branching fractions for these reactions are experimentally measured using a modified commercial ion trap mass spectrometer whose kinetic data are in good accord with those of a flowing afterglow apparatus reported here. Last, we have examined the fragmentation patterns of these deprotonated azoles to elucidate their destruction mechanisms in high-energy environments. All experimental data are supported and complemented by electronic structure calculations at the B3LYP/6-311++G(d,p) and MP2(full)/aug-cc-pVDZ levels of theory.

  2. Combinatorial Libraries of Bis-Heterocyclic Compounds with Skeletal Diversity

    Soural, Miroslav; Bouillon, Isabelle; Krchňák, Viktor

    2009-01-01

    Combinatorial solid-phase synthesis of bis-heterocyclic compounds, characterized by the presence of two heterocyclic cores connected by a spacer of variable length/structure, provided structurally heterogeneous libraries with skeletal diversity. Both heterocyclic rings were assembled on resin in a combinatorial fashion. PMID:18811208

  3. Combinatorial Libraries of Bis-Heterocyclic Compounds with Skeletal Diversity

    Soural, Miroslav; Bouillon, Isabelle; Krchňák, Viktor

    2008-01-01

    Combinatorial solid-phase synthesis of bis-heterocyclic compounds, characterized by the presence of two heterocyclic cores connected by a spacer of variable length/structure, provided structurally heterogeneous libraries with skeletal diversity. Both heterocyclic rings were assembled on resin in a combinatorial fashion.

  4. Radical C-H functionalization to construct heterocyclic compounds.

    Yu, Jin-Tao; Pan, Changduo

    2016-02-07

    Heterocyclic compounds are widely present in natural products, pharmaceuticals and bioactive molecules. Thus, organic and pharmaceutical chemists have been making extensive efforts to construct those heterocyclic frameworks through developing versatile and efficient synthetic strategies. The direct C-H functionalization via the radical pathway has emerged as a promising and dramatic approach towards heterocycles with high atom- and step-economy. Heterocyclic compounds such as coumarins, furans, benzofurans, xanthones, benzothiazoles, indoles, indolines, oxindoles, quinolines, isoquinolines, quinoxaline, and phenanthridines have been successfully synthesized by C-H functionalization through the radical pathway. In this review, recent advances on radical C-H functionalization to construct heterocyclic compounds are highlighted with discussions.

  5. Aspects and prospects of the chemistry of organic heterocycles (review)

    Schroth, W.

    1986-01-01

    The systematics of heterocycles, their place in organic chemistry, and their significance for theory and practice are discussed. Problems of the chemistry of heterocycles are discussed on the examples of systems with various types of conjugation and ring sizes. The focus is on the principles of synthesis of heterocycles, in particular, those based on acetylene, various C 3 fragments, carbon disulfide, and maleic anhydride. Individual sections of the survey are devoted to the role of heterocycles in biosynthesis, as well as certain problems common to the chemistry of heterocycles, biochemistry, and macromolecular chemistry

  6. The tert-Amino Effect in Heterocyclic Chemistry. Synthesis of Spiro Heterocycles

    Y. Morzherin

    2005-09-01

    Full Text Available The tert-amino reaction effect was examined. A new method to synthesize spiro heterocycles is presented. It was shown that the “tert-amino effect” could be applied to the formation of spiro-fused heterocycles. The formation of spiro compounds proceeds in most cases in good yields in a one-pot reaction.

  7. Microwave-Assisted Multicomponent Synthesis of Heterocycles

    Kruithof, A.; Ruijter, E.; Orru, R.V.A.

    2011-01-01

    Multicomponent reactions are valuable tools for the generation of diverse heterocycles. As in many fields or organic chemistry, microwave irradiation is rapidly replacing conventional heating methods in multicomponent chemistry. In this review, we present an overview of recent applications of the

  8. In vitro disposition profiling of heterocyclic compounds.

    Keemink, Janneke; Wuyts, Benjamin; Nicolaï, Johan; Jonghe, Steven De; Stella, Alessandro; Herdewijn, Piet; Augustijns, Patrick; Annaert, Pieter

    2015-08-01

    Compound libraries that are screened for biological activity commonly contain heterocycles. Besides potency, drug-like properties need to be evaluated to ensure in vivo efficacy of test compounds. In this context, we determined hepatic and intestinal disposition profiles for 17 heterocyclic compounds. All studied compounds showed rapid uptake in suspended rat hepatocytes, whereas metabolism was poor and the rate-limiting step in hepatic elimination. In vitro assays demonstrated a relatively low solubility and high intestinal permeability. Based on these in vitro data, heterocycles were categorized in the biopharmaceutics classification system (BCS) and the biopharmaceutics drug disposition classification system (BDDCS) to predict disposition characteristics before clinical data are available. Our findings emphasized the importance to use hepatocytes in addition to microsomes to study metabolism, since the latter lack non-microsomal enzymes and cellular context. Moreover, intracellular exposure should be considered to gain insight in the relevant fraction of the compound available at the enzymatic site. Finally, the study reveals discrepancies associated with the classification of heterocycles in BCS versus BDDCS. These probably originate from the binary character of both systems. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Sulfamides in the synthesis of heterocyclic compounds

    Gazieva, Galina A; Kravchenko, Angelina N; Lebedev, Oleg V

    2000-01-01

    A comparative analysis of the structures and physicochemical properties of sulfamides and ureas has been performed. New procedures for the synthesis of heterocyclic compounds containing the sulfamide fragment are surveyed and the properties of the resulting compounds are described. The bibliography includes 112 references.

  10. -Heterocyclic Carbene Complexes of Mineral Acids

    Brill, Marcel; Nahra, Fady; Gó mez-Herrera, Alberto; Zinser, Caroline; Cordes, David B.; Slawin, Alexandra M. Z.; Nolan, Steven P.

    2016-01-01

    We have synthesized and characterized new gold-N-heterocyclic carbene (NHC) complexes derived from the deprotonation of mineral acids. The use of sulfuric acid was a particularly interesting case. These complexes were tested in known gold-catalyzed reactions, such as the hydration of alkynes and the Meyer–Schuster rearrangement. They proved to be highly efficient in both reactions.

  11. -Heterocyclic Carbene Complexes of Mineral Acids

    Brill, Marcel

    2016-11-08

    We have synthesized and characterized new gold-N-heterocyclic carbene (NHC) complexes derived from the deprotonation of mineral acids. The use of sulfuric acid was a particularly interesting case. These complexes were tested in known gold-catalyzed reactions, such as the hydration of alkynes and the Meyer–Schuster rearrangement. They proved to be highly efficient in both reactions.

  12. Heat exchanges in nitrogen and hydrogen boiling under pressure; Echanges thermiques dans l'azote et l'hydrogene bouillant sous pression

    Roubeau, P [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1961-07-01

    The heat transfer between a horizontal wall and boiling nitrogen or hydrogen has been studied from atmospheric pressure to 2/3 of the critical pressure. The q = f(T) curves are rather well defined for nitrogen but more uncertain for hydrogen. In general, the measured {delta}T are inferior to those given by various authors using the wire method. The q{sub max} = f(P) more reproducible curves show for both fluids a maximum at about 0.4 P{sub cr} say 45 watt cm{sup -2} for 12.5 atm in nitrogen and 16 watt cm{sup -2} for 5.5 atm in hydrogen. Beyond, calefaction appears with a reduced dissipated power, rough reduction (90 per cent in few degrees) for nitrogen, smoother for hydrogen. (author) [French] On a etudie l'echange de chaleur entre une paroi horizontale et l'azote ou l'hydrogene bouillant depuis la pression atmospherique jusqu'au 2/3 de la pression critique. Les courbes q = f(T) sont assez bien definies pour l'azote mais accusent une marge d'incertitude pour l'hydrogene. En generale, les {delta}T mesurees sont inferieures a celles obtenues par divers auteurs utilisant la methode du fil. Les courbes plus reproductibles de q{sub max} f(P) passent par un maximum pour les deux liquides a environ 0,4 P{sub cr}, c'est-a-dire 45 watt cm{sup -2} pour 12,5 atm dans l'azote et 16 watt cm{sup -2} pour 5,5 atm dans l'hydrogene. Au-dela, la calefaction se produit avec un pouvoir dissipatif reduit, une reduction brusque pour l'azote (90 p. 100 en quelques degres) et plus reguliere pour l'hydrogene. (auteur)

  13. Photometabolism of Heterocyclic Aromatic Compounds by Rhodopseudomonas palustris OU 11

    Sasikala, C.; Ramana, C. V.; Rao, P. Raghuveer

    1994-01-01

    Rhodopseudomonas palustris OU 11 (ATCC 51186; DSM 7375) isolated from a pond of chemical industry effluent could anaerobically photometabolize heterocyclic aromatic compounds belonging to the pyridine and pyrazine groups only after a period of adaptation on pyrazinoic acid of 5 to 6 weeks. Growth on heterocyclic compounds was light dependent. The effects of various concentrations of heterocyclic compounds on growth suggest that higher concentrations of these compounds inhibit growth and are toxic. PMID:16349307

  14. Structural mechanisms of photoeffect in polyimide structures containing heterocyclic fragments

    Aleksandrova, E. L.

    2006-01-01

    Trends in the variation in the quantum yields of charge-carrier photogeneration in polyimide structures containing heterocyclic fragments are studied. It is shown that the efficiency of sensitization of polyimides depends on the donor and acceptor properties of the fragments of monomeric units of the polyimide. It is established that the range of spectral sensitivity for heterocyclic fragments representing intramolecular complexes with charge transport is wider than that for heterocycles that do not represent such complexes

  15. New heterocyclic compounds from Ranunculus ternatus Thunb.

    Feng, Zi-Ming; Zhan, Zhi-Lai; Yang, Ya-Nan; Jiang, Jian-Shuang; Zhang, Pei-Cheng

    2017-10-01

    Five new heterocyclic compounds, 5-α-d-fructofuranosylmethyl-furfural (1), 5-β-d-fructofuranosylmethyl-furfural (2), 5-β-d-fructopyranosylmethyl-furfural (3), 4-(2-((2S-2,3-dihydroxypropoxy)methyl)-5-formyl-1H-pyrrol-1-yl)butanoic acid (4), and 3S,4S-4,5,8-trihydroxy-3-(prop-1-en-2-yl)isochroman-1-one (5), were obtained from the root of Ranunculus ternatus Thunb., which is a traditional Chinese anti-tuberculosis medicine. Their structures were elucidated by UV, IR, HRESIMS, NMR data, and the comparison of experimental and calculated electronic circular dichroism (ECD) spectra. Notably, compounds 1-3 are rarely occurring furfural fructosides in natural sources. These heterocyclic compounds could be further studied for the synthetic chemists and pharmacologists due to the source and structural properties. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Water purification by reverse osmosis using heterocyclic polymer membranes

    Scott, H.

    1972-01-01

    Pyrrone (polyimidazopyrrolone) polymers are a new class of thermally stable, radiation and chemical resistant aromatic-heterocyclic polymers featuring a greater chemical and mechanical durability than cellulose acetate.

  17. Gestion de la fertilisation azotée des cultures de plein champ. Perspectives d'amélioration de l'efficience d'utilisation de l'azote sur base du suivi du statut azoté de la biomasse aérienne

    Goffart, JP.

    2013-01-01

    Full Text Available Nitrogen fertilization management of open-field crops. Opportunities for improvement of nitrogen use efficiency based on crop nitrogen status monitoring. The improvement of nitrogen use efficiency in crops is currently an important issue in farming due to current and future economical and environmental constraints. Splitting of N fertilizer application is the most suitable approach for providing an optimal match of N need and supply. The implementation of monitoring methods to assess crop N status is required to define the relevant amounts and periods required for split applications. This paper discusses the available methods of split N fertilizer application and their mode of use and implementation. After a short overview of the concept of crop N status, the main existing methods to estimate nitrogen needs are examined for their accuracy, specificity and sensitivity based on research conducted at CRA-W (Production and Sectors Department, Crop Production Systems Unit over the last two decades, focusing specifically on the potato crop. The methods and the results described relate to the petiole sap nitrate concentration test assessed via a reflectometer, the measurement of leaf chlorophyll concentration with a handheld chlorophyll meter, leaf chlorophyll fluorescence readings with handheld fluorimeters, and the measurement of crop light reflectance with a handheld radiometer (ground-based remote sensing or with satellite imagery (spatial remote sensing. Conditions for implementing such methods within decision support systems are briefly described, by focusing on the need to use relative values rather than raw values taken from the readings, and also on the requirement for threshold value definition. The integration of crop nitrogen status values into N fertilization recommendation models is illustrated through a Decision Support System created at CRA-W for the potato crop.

  18. Effet de la complémentation azotée sur les performances zootechniques de la chèvre locale

    Mahouachi, M.

    2006-01-01

    Full Text Available Effects of Supplementing Grazing by Different Sources of Protein on Tunisian Goat Performances. The effects of supplementing grazing by one of three sources of protein: barley, barley + soya bean, or barley + soya bean treated with formaldehyd, were studied on body weight evolution, milk production (yield and components, and on N-NH3 concentration in the rumen juice of female goats and on growing kids. Forty-five females of the local tunisian breed were used in the experiment. All females were in the first 15 weeks of lactation. Animals were divided into three groups (1st, 2nd and 3rd of 15 animals each. Groups were homogeneous with respect to age, lactation rank, milk yield in the first test day, and litter size. Each animal received 500 g of vetch-oat hay and 500 g of barley, barley + soya bean, or barley + treated soya bean in the 1st, 2nd and 3rd group, respectively, in addition to pasture. Protein supplementation affected (P< 0.05 growth of goat kids (116 g/day and 94 g /day for 3rd and 1st group, respectively, milk yield (88.1 l and 67.1 l for the 3rd and 1st group, respectively, and fat percentage of milk (5.2% and 4.2% for the 3rd and 1st group, respectively. The N-NH3 concentration was higher (P< 0.05 in the rumen juice of animals fed untreated soya bean than those fed treated soya bean.

  19. Effets du fractionnement de l'azote uréique en présence de Phosphore et de Potassium sur culture du maïs

    Ndikumana, L.

    1987-01-01

    Full Text Available Maize's response to fractionnated application of urea nitrogen in edaphoclimatic conditions of Yangambi (Zaire. Studies have been conducted to establish the nutritional characteristics of three cultivars of the winged bean (Psophocarpus tetragonolobus (L. DC. Protein, lipid, amino acids and mineral compositions of the beans have been determined. The protein and fat contents were 37 to 40 % and 16 to 22 % respectively. Defatted beans meal had a very high protein content (47-49 %. The average mineral levels in the seeds, expressed as g/kg DM, were 6.6g, 1.6g, 0.08g and 0.06g for phosphorus, calcium, iron and zinc respectively. The amino acids profile revealed very high levels of aspartic acid, glutamic acid, lysine, arginine, leucine and threonine as compared to these of soybean protein. Sulfur amino acids levels are low.

  20. Les effets et conséquences de la méthanisation sur la matière organique et l’azote des lisiers de porc

    QUIDEAU, Pierre

    2013-10-01

    Full Text Available Les technologies liées au procédé de méthanisation se développent depuis peu. Elles transforment les substrats organiques utilisés, modifiant plus ou moins leurs caractéristiques et leurs impacts environnementaux. L’analyse du cas du lisier de porc illustre ces modifications et leurs conséquences.

  1. Palladium-catalyzed allylation of tautomerizable heterocycles with alkynes.

    Lu, Chuan-Jun; Chen, Dong-Kai; Chen, Hong; Wang, Hong; Jin, Hongwei; Huang, Xifu; Gao, Jianrong

    2017-07-21

    A method for the allylic amidation of tautomerizable heterocycles was developed by a palladium catalyzed allylation reaction with 100% atom economy. A series of structurally diverse N-allylic substituted heterocycles can be synthesized in good yields with high chemo-, regio-, and stereoselectivities under mild conditions.

  2. Alkynylation of heterocyclic compounds using hypervalent iodine reagent.

    Kamlar, M; Císařová, I; Veselý, J

    2015-03-14

    The alkynylation of various nitrogen- and/or sulphur-containing heterocyclic compounds using hypervalent iodine TMS-EBX by utilization of tertiary amines under mild conditions is described. The developed metal-free methodology furnishes the corresponding alkynylated heterocycles bearing quaternary carbon in high yields.

  3. Synthesis of boron-containing heterocyclic compounds

    Azev, Yuri; Slepukhina, Irina; Gabel, Detlef

    2004-01-01

    The synthesis of boron-containing 1,3,5-triazines and 1,2,4-triazines is described. Derivatives of 1,3,5-triazine containing the o-carborane cluster have been obtained by reacting the corresponding propargyl derivatives with B 10 H 14 . Derivatives of 1,2,4-triazine containing the B 12 H 12 2- cluster have been obtained by nucleophilic substitution of ethylsulfone derivatives with B 12 H 11 SH 2- . They have been isolated in their ring-protonated form. Reaction of RNH 2 -B 8 H 11 NH-R with stericly demanding heterocycles failed, either for steric or for solubility reasons

  4. Sulfur ylides in the synthesis of heterocyclic and carbocyclic compounds

    Lakeev, Sergei N; Maydanova, Irina O; Galin, Fanur Z; Tolstikov, Genrikh A

    2001-01-01

    Data on the use of sulfonium ylides in the synthesis of carbocyclic and heterocyclic compounds published over the last 15 years are analysed, systematised and generalised. The bibliography includes 139 references.

  5. New heterocyclic compounds: Synthesis and antitrypanosomal properties.

    Pomel, S; Dubar, F; Forge, D; Loiseau, P M; Biot, C

    2015-08-15

    Three new series of quinoline, quinolone, and benzimidazole derivatives were synthesized and evaluated in vitro against Trypanosoma brucei gambiense. In the quinoline series, the metallo antimalarial drug candidate (ferroquine, FQ) and its ruthenium analogue (ruthenoquine, RQ, compound 13) showed the highest in vitro activities with IC50 values around 0.1 μM. Unfortunately, both compounds failed to cure Trypanosoma brucei brucei infected mice in vivo. The other heterocyclic compounds were active in vitro with IC50 values varying from 0.8 to 34 μM. One of the most interesting results was a fluoroquinolone derivative (compound 2) that was able to offer a survival time of 8 days after a treatment at the single dose of 100 μmol/kg by intraperitoneal route. Although no clear-cut structure-activity relationships emerged, further pharmacomodulations are worth to be developed in this series. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Effect of Nitrogen Fertilizer on Variations in Composition in Protein and Non-Protein Compounds in the Aerial Parts of Dactylis Glomerata L; Influence de la Fertilisation Azotee sur les Variations de la Composition en Composes Proteiques et Non Proteiques des Parties Aeriennes de Dactylis Glomerata L.

    Lefebvre, J. M. [Institut National de la Recherche Agronomique, Station d' Agronomie, Dijon (France)

    1968-07-01

    fertilisations azotees a des rythmes d'apports differents. L'enrichissement en azote organique soluble, amino-acides, amides, peptides simples, et en composes proteiques est sensiblement proportionnel a la dose d'azote apportee dans les differents cycles vegetatifs. L'azote mineral libre, compose a peu pres exclusivement de nitrates, presente des valeurs elevees, surtout dans les premiers cycles vegetatifs se situant a un moment ou les temperatures basses ne favorisent pas une reduction rapide. Les valeurs trouvees augmentent avec les quantites d'azote fournies aux plantes. Si la fertilisation azotee est apportee sur la graminee quinze jours apres la coupe des parties aeriennes et non immediatement comme cela se fait habituellement dans la pratique agricole, on observe une modification complete des phenomenes de synthese proteique. En effet, dans ce cas la reduction des nitrates est tres rapide et la metabolisation en composes organiques solubles et condenses importante. De ce fait, on n'observe pas d'accumulations transitoires elevees de nitrates dans les cycles vegetatifs d'ete et d'automne. D e plus, ce qui est tres important pour la qualite alimentaire du produit recolte, les teneurs en proteines brutes sont beaucoup plus elevees (de 5 0 % environ) a la fin du cycle pour une m 6me quantite d'azote apportee a la fertilisation. Les composes azotes organiques solubles, amino-acides et amides, sont egalement en quantite plus elevees. (author)

  7. Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

    2016-01-01

    Summary Multicomponent reactions (MCRs) are one of the most important processes for the preparation of highly functionalized organic compounds in modern synthetic chemistry. As shown in this review, they play an important role in organophosphorus chemistry where phosphorus reagents are used as substrates for the synthesis of a wide range of phosphorylated heterocycles. In this article, an overview about multicomponent reactions used for the synthesis of heterocyclic compounds bearing a phosphonate group on the ring is given. PMID:27559377

  8. Influence des engrais de type NPK sur l’oviposition d’Aedes aegypti

    Darriet F.

    2008-03-01

    Full Text Available Les engrais sont des associations de minéraux destinées à apporter aux plantes des compléments nutritifs nécessaires à leur croissance. Les engrais modernes de type NPK combinent les trois éléments de base que sont l’azote (N, le phosphore (P et le potassium (K. Dans cette étude de laboratoire réalisée dans des tunnels expérimentaux, nous avons étudié l’influence de solutions aqueuses contenant différentes concentrations en engrais NPK sur l’oviposition de femelles d’Aedes aegypti. Les résultats ont montré que les solutions contenant les concentrations en NK = 17-33 mg/l et P = 23-47 mg/l attiraient significativement plus de femelles gravides que l’eau osmosée seule (P 0,05. Ces résultats suggèrent que certaines teneurs en engrais NPK peuvent influencer le comportement de ponte du moustique Ae. aegypti.

  9. Altiplano Sur de Bolivia

    Alvarez-Flores, Ricardo; Bommel, Pierre; Bourliaud, Jean; Chevarria Lazo, Marco; Cortes, Geneviève; Cruz, Pablo; Del Castillo, C.; Gasselin, Pierre; Joffre, Richard; Leger, Francois; Nina Laura, Juan Peter; Rambal, Serge; Rivière, Gilles; Tichit, Muriel; Tourrand, Jean-François

    2014-01-01

    Alimento de base de las poblaciones andinas desde hace milenios, la quinua se ha convertido hoy en un producto apreciado en el mercado internacional de alimentos dietéticos, orgánicos y equitativos. Este cambio lo iniciaron los mismos productores del Altiplano Sur de Bolivia hace aproximadamente unos 40 años. En medio de un desierto de altura, ellos lograron desarrollar una floreciente producción agrícola de exportación. Aunque cuentan con lucrativos nichos de mercado, los productores de quin...

  10. METHODS OF SYNTHESIS EIGHT-TELLURIUM-CONTAINING HETEROCYCLES WITH MORE HETEROATOMS

    G. M. Abakarov

    2013-01-01

    Full Text Available In this article systematized and summarized data on the synthesis of neweight-embered tellurium-containing heterocycles and new preparative methods described above produce heterocyclic tellurium.

  11. Thiosemicarbazides in the synthesis of five- and six-membered heterocyclic compounds

    Gazieva, Galina A; Kravchenko, Angelina N

    2012-01-01

    Data on key chemical transformations of thiosemicarbazides resulting in heterocyclic compounds are generalized and described systematically. Methods for the synthesis of five- and six-membered heterocycles with two and three heteroatoms are considered. The bibliography includes 190 references.

  12. MICROBIAL DEGRADATION OF NITROGEN, OXYGEN AND SULFUR HETEROCYCLIC COMPOUNDS UNDER ANAEROBIC CONDITIONS: STUDIES WITH AQUIFER SAMPLES

    The potential for anaerobic biodegradation of 12 heterocyclic model compounds was studied. Nine of the model compounds were biotransformed in aquifer slurries under sulfate-reducing or methanogenic conditions. The nitrogen and oxygen heterocyclic compounds were more susceptible t...

  13. Microwave-assisted synthesis of bio-active heterocycles in aqueous media

    Polshettiwar, Vivek; Varma, Rajender S.

    2010-01-01

    Synthesis of bio-active heterocycles and fine chemicals in aqueous media are one of the best solutions for the development of green and sustainable protocols. To illustrate the advantages of aqueous MW chemistry in heterocycle synthesis

  14. Heterocyclic amines in meat and meat products

    Aliye BULGAN

    2013-06-01

    Full Text Available Heterocyclic amines (HA are the mutagenic/carcinogenic compounds which generate as a result of cooking of red meat, poultry meat and fish fillets at high temperatures. Up to 20 different HAs were detected and classified in the researches that conducted on these types of meats cooked at high temperatures. HAs are the products of Maillard reactions and the Strecker degredation of main precursors such as creatine/creatinine, aminoacid and the polysaccharides. Many physical and chemical factors effect the formation of HAs. Thus, it was reported by many researchers that utilizing coating and marination processes in addition to using natural and synthetic antioxidants and seasonings-plant extracts were effective on inhibiting/decreasing the formation of HAs. Additionally, boiling/steaming and microwave cooking methodologies were recommended instead of barbecuing, grilling or frying to inhibit/decrease the formation of HAs. The HAs formed in meat and meat products and the factors which have effects on the formation of HAs are presented in this review.

  15. Recent advances in the electrochemical construction of heterocycles

    Robert Francke

    2014-12-01

    Full Text Available Due to the fact that the major portion of pharmaceuticals and agrochemicals contains heterocyclic units and since the overall number of commercially used heterocyclic compounds is steadily growing, heterocyclic chemistry remains in the focus of the synthetic community. Enormous efforts have been made in the last decades in order to render the production of such compounds more selective and efficient. However, most of the conventional methods for the construction of heterocyclic cores still involve the use of strong acids or bases, the operation at elevated temperatures and/or the use of expensive catalysts and reagents. In this regard, electrosynthesis can provide a milder and more environmentally benign alternative. In fact, numerous examples for the electrochemical construction of heterocycles have been reported in recent years. These cases demonstrate that ring formation can be achieved efficiently under ambient conditions without the use of additional reagents. In order to account for the recent developments in this field, a selection of representative reactions is presented and discussed in this review.

  16. Blue Chitin columns for the extraction of heterocyclic amines from urine samples

    Bang, J.; Frandsen, Henrik Lauritz; Skog, K.

    2004-01-01

    During normal cooking of meat, a class of mutagenic/carcinogenic compounds called heterocyclic amines is formed. Heterocyclic amines are rapidly absorbed and metabolised in the human body, and for estimation of the intake of heterocyclic amines, it is useful to determinate their levels in the uri...

  17. An automatic device for refilling liquid nitrogen traps at constant time intervals; Dispositif automatique assurant le remplissage de pieces en azote liquide a intervales de temps constant

    Bourguillot, R; Lohez, P [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    We have been led to study the design of an automatic device for the filling of liquid nitrogen traps at constant time intervals in connection with the maintenance of a type MS 5 mass spectrometer; in the tube of this apparatus it is necessary to maintain a vacuum of about 10{sup -7} mm of mercury. The replenishing is done every four hours. The presence in the vacuum section of an electron multiplier has led us to provide a safety-device making it impossible for mercury vapour to come into contact with either the copper tube or the multiplier in the event of an incident leading to the warming up of the traps. In case of a breakdown, the vacuum section is therefore brought up to atmospheric pressure by the introduction of nitrogen. (author) [French] Nous avons ete conduits pour la maintenance d'un spectrometre de masse type MS 5, dans le tube duquel il faut entretenir un vide de quelques 10{sup -7} mm de mercure, a etudier un systeme de remplissage automatique a intervalle de temps fixe des pieges en azote liquide. Ce remplissage se fait toutes les quatre heures. La presence dans l'enceinte sous vide, d'un multiplicateur d'electrons, nous a amenes a prevoir un systeme de securite evitant de mettre le tube en cuivre et le multiplicateur en contact avec la vapeur de mercure en cas d'incident amenant le rechauffage des pieges. En cas de panne, l'enceinte sous vide est donc ramenee a la pression atmospherique par une introduction d'azote. (auteur)

  18. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...... versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

  19. Inorganic heterocycles with two manganes or rhenium carbonyl units

    Kuellmer, V.; Vahrenkamp, H.

    1977-01-01

    From the reactive complexes [(CO) 4 M-E-Sn(CH 3 ) 3 ] 2 (M = Mn,Re; E = S,Se) with (CH 3 ) 2 PCl via the non-isolable four-membered ring intermediates [(CO) 4 M-E-P(CH 3 ) 2 ] 2 the six-membered heterocycles[-(CO) 4 M-P(CH 3 ) 2 -E-] 2 are formed. By use of (CH 3 ) 2 AsCl both the four-membered ring intermediates and the six-membered ring products can be isolated. The six-membered heterocycles can be opened by trimethylphosphine. (orig./HK) [de

  20. Synthesis and Characterization of a New Heterocyclic Azo Pigment

    Asniza, M.; Issam, A.M.; Khalil, H.P.S.A.

    2011-01-01

    A new heterocyclic coupling agent has been produced from the reaction of maleic anhydride and p-aminophenol, namely N-(4-hexahydrophenol)maleimide. The coupling agent underwent azo coupling reaction with aromatic amine, which is p-aminophenol to produce a new heterocyclic azo pigment. The pigment was then subjected to solubility, hiding power and light fastness test. Fourier Transform Infrared Spectroscopy (FTIR), Ultraviolet/ Visible (UV/Vis) Spectroscopy, and Nuclear Magnetic Resonance Spectroscopy ( 1 H-NMR, 13 C-NMR) were used to obtain the characteristics and structural features of the pigment. (author)

  1. Combinatorial synthesis of oxazol-thiazole bis-heterocyclic compounds.

    Murru, Siva; Nefzi, Adel

    2014-01-13

    A combinatorial library of novel oxazol-thiazole bis-heterocycles was synthesized in good to excellent overall yields with high purity using a solution and solid-phase parallel synthesis approach. Oxazole amino acids, prepared from serine methyl ester and amino acids via coupling and cyclodehydration, were treated with Fmoc-NCS and α-haloketones for the parallel synthesis of diverse bis-heterocycles. Fmoc-isothiocyanate is used as a traceless reagent for thiazole formation. Oxazole diversity can be achieved by using variety of amino acids, whereas thiazole diversity is produced with various haloketones.

  2. Antioxidant evaluation of heterocyclic compounds by cytokinesis-block micronucleus assay.

    Godevac, Dejan; Tesević, Vele; Vajs, Vlatka; Milosavljević, Slobodan; Stanković, Miroslava

    2013-03-01

    This article summarizes the results of using cytokinesis-block micronucleus (CBMN) assay to evaluate the antioxidant potential of heterocyclic compounds. Most studies were carried out with naturally occurring heterocyclic compounds such as plant polyphenols: flavonoids, xanthones, coumarins, and ellagitannins, or plant derived products (juices, extracts, supplements) rich in bioactive heterocyclic compounds. There are also some studies dealing with synthetic heterocyclic antioxidants. CBMN assay is an in vitro study that has been used to evaluate antioxidant and protective effects of heterocyclic compounds on induced chromosome aberration in human lymphocytes.

  3. Signature isotopique du carbone et de l'azote dans la matière organique particulaire de la glace de mer en Arctique : facteurs de contrôle et applications écologiques

    Pineault, Simon

    2011-01-01

    L'objectif de mon étude était de décrire la dynamique des isotopes stables du carbone et de l'azote de la matière organique particulaire sympagique pendant la transition printanière en mer de Beaufort. La biomasse de protistes et la disponibilité en carbone inorganique dissous ont été identifiées comme principaux facteurs de contrôle du signal isotopique du carbone à la base de la glace annuelle. Les signatures isotopiques de l'azote n'ont pu être expliquées à l'aide des variables mesurés. Un...

  4. Greener Alternatives to Expedient Synthesis of Heterocycles and Nanomaterial

    A brief account of reactions involving microwave (MW) exposure of neat reactants or catalyzed by mineral support surfaces, such as alumina, silica, clay, or their ‘doped’ versions, for the rapid one-pot assembly of heterocyclic compounds [1] from in situ generated reactive interm...

  5. Greener Synthetic Alternatives to Heterocycles, Nanomaterials and Nanocomposites

    Microwave (MW) expedited reaction of neat reactants or catalyzed by mineral support surfaces, such as alumina, silica, clay, or their ‘doped’ versions, for the rapid one-pot assembly of heterocyclic compounds from in situ generated reactive intermediates via enamines or using hyp...

  6. Transformation of saturated nitrogen-containing heterocyclic compounds by microorganisms.

    Parshikov, Igor A; Silva, Eliane O; Furtado, Niege A J C

    2014-02-01

    The saturated nitrogen-containing heterocyclic compounds include many drugs and compounds that may be used as synthons for the synthesis of other pharmacologically active substances. The need for new derivatives of saturated nitrogen-containing heterocycles for organic synthesis, biotechnology and the pharmaceutical industry, including optically active derivatives, has increased interest in microbial synthesis. This review provides an overview of microbial technologies that can be valuable to produce new derivatives of saturated nitrogen-containing heterocycles, including hydroxylated derivatives. The chemo-, regio- and enantioselectivity of microbial processes can be indispensable for the synthesis of new compounds. Microbial processes carried out with fungi, including Beauveria bassiana, Cunninghamella verticillata, Penicillium simplicissimum, Aspergillus niger and Saccharomyces cerevisiae, and bacteria, including Pseudomonas sp., Sphingomonas sp. and Rhodococcus erythropolis, biotransform many substrates efficiently. Among the biological activities of saturated nitrogen-containing heterocyclic compounds are antimicrobial, antitumor, antihypertensive and anti-HIV activities; some derivatives are effective for the treatment and prevention of malaria and trypanosomiasis, and others are potent glycosidase inhibitors.

  7. Toxicity of six heterocyclic nitrogen compounds to Daphnia pulex

    Perry, Cynthia M.; Smith, Stephen B.

    1988-01-01

    We determined the relative toxicities to the aquatic crustacean Daphniz pulex of six heterocyclic nitrogen compunds. These compounds were selected because they were detected in lake trout or walleyes and were commercially available. Stress to the daphnid populations may affect forage fish populations that depend either directly or indirectly on zooplankton as a food source in the Great Lakes.

  8. GREENER SYNTHESIS OF HETEROCYCLIC COMPOUNDS USING MICROWAVE IRRADIATION

    An introduction of our interest in the microwave-assisted greener synthesis of a variety of heterocyclic compounds will be presented. It involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of recyclable mineral supports, such as alumina, sili...

  9. Alkoxy(alkyl)silylalkyl derivatives of nitrogen-containing heterocycles

    Trofimova, Ol'ga M; Voronkov, Mikhail G; Chernov, Nikolai F

    1999-01-01

    The published data on the synthesis, properties and transformations of alkoxy(alkyl)silylalkyl derivatives of nitrogen-containing heterocycles of the general formula Het(CH 2 ) n SiX 3 are surveyed and systematised. Data on the biological activities and applications of these compounds are presented. The bibliography includes 255 references.

  10. Synthesis and properties of heterocyclic type I photoinitiators

    Liska, R.; Knaus, S.; Wendrinsky, J.

    1999-01-01

    The synthesis and properties of a series of new heterocyclic hydroxyalkylphenone-analogous photoinitiators (PIs) is described. The PIs are obtained by reaction of aromatic organolithium compounds with nitriles or by Friedel-Craft's-acylation. Preliminary photocalorimetric tests and UV absorption data are included

  11. Greener and Expeditious Synthesis of Bioactive Heterocycles using Microwave Irradiation

    The utilization of green chemistry techniques is dramatically reducing chemical waste and reaction times as has recently been proven in several organic syntheses and chemical transformations. To illustrate these advantages in the synthesis of bio-active heterocycles, we have stud...

  12. 40 CFR 721.10003 - Manganese heterocyclic tetraamine complex (generic).

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Manganese heterocyclic tetraamine complex (generic). 721.10003 Section 721.10003 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... section. (2) The significant new uses are: (i) Industrial, commercial, and consumer activities...

  13. synthesis and characterization of some poly functionalized heterocyclic derivatives of expected biological activity

    El-sayed, M.S.

    2001-01-01

    The present work was aimed and designed to fulfil The following objectives : 1- Continuation of the effort done by our research group in the field of chemistry of pyridinethione derivatives and their biological activities. 2- Synthesis of several new heterocyclic derivatives containing N and/or S using the laboratory available reagents. 3- Establishment of the structures of the newly synthesized heterocyclic compounds by the data of IR, 1 H-NMR, mass spectra in addition to the elemental analysis. 4- Synthesis of some of these heterocyclic derivatives via alternative routs and this used as a tool to confirm the structures of the newly synthesized heterocyclic derivatives. 5- study of the most probable mechanisms leading to the formation of the new heterocyclic derivatives. 6- The antimicrobial activity of some of the newly synthesized heterocyclic derivatives was tested against several types of organisms

  14. Synthesis and antibacterial activity of some heterocyclic derivatives of sulfanilamide

    B.B. Subudhi

    2012-12-01

    Full Text Available Considering the promising antimicrobial potential of carbonic anhydrase inhibitors and heterocyclic compounds some heterocyclic derivatives of sulfanilamide (2a-e were synthesized. The diazotisation of sulfanilamide followed by substitution with ethylacetoacetate and further condensation yielded compounds 2a-c. Schiff base of sulfanilamide with salicylaldehyde on reaction with thioglycollic acid and chloroacetyl chloride resulted in compound 2d-e. The susceptibility of Staphylococcus aureus, Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa to the title compounds (300 μg/disc was investigated and compared to that of nitrofurantoin (300 μg/disc and ciprofloxacin (25 μg/disc. The title compounds showed good antimicrobial activity.DOI: http://dx.doi.org/10.4314/bcse.v26i3.15

  15. Biotransformation of heterocyclic dinitriles by Rhodococcus erythropolis and fungal nitrilases

    Vejvoda, Vojtěch; Šveda, Ondřej; Kaplan, Ondřej; Přikrylová, Věra; Elišáková, Veronika; Himl, Michal; Kubáč, David; Pelantová, Helena; Kuzma, Marek; Křen, Vladimír; Martínková, Ludmila

    2007-01-01

    Roč. 29, č. 7 (2007), s. 1119-1124 ISSN 0141-5492 R&D Projects: GA AV ČR IAA500200708; GA MŠk LC06010; GA MŠk OC D25.001 Institutional research plan: CEZ:AV0Z50200510 Keywords : amidase * arpegillus nniger * heterocyclic Subject RIV: EE - Microbiology, Virology Impact factor: 1.222, year: 2007

  16. Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

    Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

    1985-01-01

    Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

  17. Photoactivation of heterocyclic change-transfer complexes-electrolytes

    Studzinskij, O.P.; Ponomareva, R.P.; Proskuryakova, T.V.

    1999-01-01

    Effect of light on the systems containing of five- or six-number nitrogen-containing heterocycles, molecular iodine and different-nature organic solvents, has been studied by the methods of absorption spectroscopy and electric conductivity measurement. It has been ascertained that in proton-donor solvents the complexes of 1:1 composition are formed with charge transfer, their electric conductivity increasing essentially with photoactivation [ru

  18. Ruthenium sulfoxides structure and reactivity with nitrogen heterocyclic bases

    Oliveira, Denise de.

    1990-01-01

    Ruthenium (II) sulfoxides are compounds of great interest in oxidative catalysis and in chemotherapy. In order to contribute for the understanding of the chemistry and electronic structure of this class of compounds, it has been studied a series of [Ru Cl 2 (S-DMSO) 2 L x ] complexes, where x = 1 (polymeric compounds) or 2 (monomers) and L N-heterocyclic ligands (pyridine, pyrazine and imidazole derivatives). The nature of N-heterocyclic ligand and their coordination are of great relevance to the stability, spectroscopic and electrochemical characteristics of the complexes. The trans-interactions are extremely important in this series, influencing the strength of the Ru(II)-> S-DMSO and Ru(II)-> L π-back donation. The DMSO and L ligands are π-acceptors. The metal-> ligand π-back donation is strengthened when the ligand is trans to chloride, which is π-donor, due to trans-cooperative interactions of the type: π-donor -> Ru(II) π-acceptor. Another interesting aspect in the series of [Ru Cl 2 (S-DMSO) 2 L 2 ] complexes is the occurrence of dissociative equilibria in the solution, due to the existence of three types of ligands. It was observed that the trans-N isomer of 2,6-dimethyl pyrazine derivative undergoes thermal substitution, with preferential liabilization of the N-heterocyclic ligand. Chloride ion is the most inert ligand in this complex. (author). 145 refs., 76 figs., 21 tabs

  19. Partitioning-separation of metal ions using heterocyclic ligands

    Hudson, M.J.; Drew, M.G.B.; Iveson, P.B.; Russell, M.L.

    2001-01-01

    Some guidelines are proposed for the effective design of heterocyclic ligands for partitioning because there is no doubt that the correct design of a molecular extractant is required for the effective separation of metal ions such as actinides(III) from lanthanides(III). Heterocyclic ligands with aromatic ring systems have a rich chemistry, which is only now becoming sufficiently well understood in relation to the partitioning process. The synthesis, characterisation and structures of some chosen molecules will be introduced in order to illustrate some important features. For example, the molecule N-carboxy-butyl-2-amino-4,6-di (2-pyridyl)-1,3,5-triazine (BADPTZ), which is an effective solvent extraction reagent for actinides and lanthanides, has been synthesised, characterised and its interaction with lanthanide ions studied. The interesting and important features of this molecule will be compared with those of other heterocyclic molecules such as 2,6-bis(5-butyl-1,2,4-triazole-3-yl) pyridine (DBTZP), which is a candidate molecule for the commercial separation of actinides and lanthanide elements. (author)

  20. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  1. Nucleobases in Space: Laboratory Studies of Polycyclic Aromatic Nitrogen Heterocycles

    Elsila, Jamie; Mattioda, Andy; Bernstein, Max; Sandford, Scott; Hudgins, Doug

    2005-01-01

    Polycyclic Aromatic Nitrogen Heterocycles (PANHs) are heterocyclic aromatics Le., PAHs with carbon atoms replaced by a nitrogen atom. These molecules have been detected in meteorite extracts, and in general these nitrogen heterocycles are of astrobiological interest since this class of molecules include nucleobases, basic components of our nucleic acids. These compounds are predicted to be present in the interstellar medium and in Titan tholin, but have received relatively little attention. We will present spectra and reactions of PANHs, frozen in solid H2O at 12 K, conditions germane to astronomical observations. In contrast to simple PAHs, that do not interact strongly with solid H2O, the nitrogen atoms in PANHs are potentially capable of hydrogen bonding with H20 changing their spectra, complicating their remote detection on the surfaces of icy bodies. Moreover, we have studied the photo-chemistry of these interesting compounds under astrophysical conditions and will use our lab studies to assess a potential interstellar heritage of these compounds in carbonaceous chondrites.

  2. The reactions of anthronylidene carbene with some heterocyclic compounds

    Divisia, Bernadette

    1970-01-01

    The action of the anthronylidene carbene, generated by photochemical decomposition of 9-diazo 10-anthron, on four heterocyclic compounds (furan, thiophene, 1-methyl-pyrrole and 2,5-dihydrofuran) has been examined. Two classical carbene reactions have been observed: the addition on double bond (furan, thiophene, 1-methylpyrrole) and hydrogen atom abstraction of the heterocyclic compound (2,5-dihydrofuran). In the case of furan and thiophene, the cyclo-propanic compound resulting from the addition is spontaneously transformed into an ethylenic derivative by valence isomerization. The furan derivative undergoes a cis-trans isomerization, while the thiophene one undergoes an extra carbene attack. In the case of 1-methylpyrrole, the corresponding cyclo-propanic compound undergoes a ring cleavage, followed by a hydrogen atom migration leading to the formation of a substituted anthron. Only an allylic hydrogen atom selective abstraction of heterocyclic compound takes place in the reaction of anthronylidene carbene with 2,5-dihydrofuran. The asymmetrical coupling of radicals so obtained yields the corresponding substituted anthron. (author) [fr

  3. Studies in Petroleum Composition the Distribution of Nitrogen Species, Metals and Coke Precursors During High Vacuum Distillation of Petroleum Étude de composition du pétrole Répartition des espèces azotées, des métaux et des précurseurs du coke pendant la distillation sous vide poussé du pétrole

    Long R. B.

    2006-11-01

    tudie cette question et tente de décrire l'influence d'une distillation approfondieà +1289 °F (environ 698 °C sur la composition en produits volatils/non volatils d'un résidu obtenu à + 950 °F (510 °C. A +1289 °F, la distillation concentre dans la fraction obtenue la majorité de l'azote, du nickel, du vanadium et des produits de tête. Cependant, étant donné le niveau élevé de son point de coupe, cette procédure implique virtuellement que certaines molécules contenant des hétéroatomes seront volatiles au point de coupe. Des quantités significatives de ces produits se trouvent dans la fraction 950-1289 °F. Parmi ceux d'entre eux qui contiennent de l'azote, on pourra trouver des benzophénanthrolines et des benzocarbazoles alkylés dont les points d'ébullition se situent dans le domaine 950-1289 °F. Il n'est pas non plus surprenant de trouver dans cette fraction des métaux volatils, puisque les organométalliques se vaporisent vers 1100 °F (environ 593 °C. Les matériaux du domaine A-1289 °F ont donné des rendements élevés en pentane- et heptane- -asphaltènes. Le bilan des poids des asphaltènes sur la base A-950 °F fait apparaître des quantités excessives d'asphaltènes dans le domaine A-1289 °F dépassant la marge d'erreurs permise dans la technique de désalphatage. On a également noté des déséquilibresen asphaltène comparables, lorsque des matières lourdes sont fractionnées par un désalphatage séquentiel utilisant des hydrocarbures différents à chaque étape (13. On peut penser que la technique d'adsorption, comme le désalphatage séquentiel, rompt les forces intermoléculaires qui, autrement, pourraient rendre les constituants de la charge solubles dans les hydrocarbones, du fait de la nature non polaire des participants. Dans le cas présent, on peut penser que les forces intermoléculaires du A-1289 °F sont plus difficiles à rompre par les n-paraffines (ou par le toluène du fait de l'absence relative (par rapport à A-950

  4. Production des micro-algues des claires ostréicoles en relation avec l'azote organique dissous excrété par les huîtres

    Robert, Jean-michel; Maestrini, Serge; Heral, Maurice; Zanette, Yvan

    1981-01-01

    L'utilisation de tests biologiques dans l'étude de la fertilité des eaux de claires ainsi que l'analyse chimique des réserves en sels nutritifs des mêmes eaux montrent qu'une part importante de la biomasse micro-algale peut être produite dans ces bassins, par assimilation par les cellules de substances organiques dissoutes. Ainsi, pour l'azote, des estimations indirectes aboutissent à des quantités de cet élément assimilé sous forme organique variant entre 0,6 et 30,7 µg-at.I-1 selon les mode...

  5. Evolution saisonnière des phosphates et des composés minéraux dissous de l'azote en lagune Aby (Côte d'Ivoire)

    Métongo, B.S.

    1989-01-01

    Cette étude présente le cycle annuel des variations des orthophosphates (P-PO4) et des composés minéraux dissous de l'azote (N-NO3, N-N02 and N-NH4) dans la colonne d'eau de juillet 1984 à juillet 1985 en lagune Aby... Les valeurs maximales des sels nutritifs sont enregistrées en saison de pluies et de crues et leur distribution est fonction de la stratification physique des eaux

  6. Programme de Gestion Durable de l'Azote en agriculture. Considérations pratiques et conceptuelles sur la méthodologie du contrôle public du reliquat d'azote nitrique dans le sol des exploitations agricoles wallonnes

    Vandenberghe, C.

    2012-01-01

    Full Text Available Implementation of the Nitrates Directive. Analysis of the assessment's methodology for the control of the soil nitrate nitrogen residue in the farm's fields of Wallonia. Within the Walloon Action Programme, transposition of the Nitrates Directive, the Administration organizes each year a control of the soil nitrate nitrogen residues in about 900 parcels located in vulnerable zone in order to verify if the practices of nitrogen spreading by the farmers are in accordance with the Walloon Action Programme. The current method is to yearly spot "suspects" by a control in three parcels in about 300 farms and to follow "suspects" by an observation programme wich leads after maximum six years to a penalty or to the end of this programme. The present statistical study means to assess the public control's methodology: what is the probability to penalize a "good" farmer, to forget a "bad" farmer? This study is based on real data and on a theoretical approach. Both conclusions indicate that the official methodology is sufficiently appropriate.

  7. The Depolymerization of Poly(Ethylene Terephthalate) (PET) Using N-Heterocyclic Carbenes from Ionic Liquids

    Kamber, Nahrain E.; Tsujii, Yasuhito; Keets, Kate; Waymouth, Robert M.; Pratt, Russell C.; Nyce, Gregory W.; Hedrick, James L.

    2010-01-01

    The depolymerization of the plastic polyethylene terephthalate (PET or PETE) is described in this laboratory procedure. The transesterification reaction used to depolymerize PET employs a highly efficient N-heterocyclic carbene catalyst derived from a commercially available imidazolium ionic liquid. N-heterocyclic carbenes are potent nucleophilic…

  8. Synthesis and antiacetylcholinesterase activity of new D-glyceraldehyde heterocyclic derivatives

    Scorzo, Cecilia M.; Fascio, Mirta L.; D'Accorso, Norma B.; Cabrera, Margarita Gutierrez; Saavedra, Luis Astudillo

    2010-01-01

    We report herein the convenient procedures for the syntheses of different heterocyclic compounds from 2,3-O-isopropylidene-D-glyceraldehyde using intramolecular cyclization, 1,3-dipolar cycloaddition or bimolecular coupling reactions. The products were characterized by 1 H and 13 C NMR spectroscopy and elemental analysis. The new heterocycles and their derivatives were evaluated as inhibitors of acetylcholinesterase enzyme. (author)

  9. Gold-catalyzed heterocyclizations in alkynyl- and allenyl-β-lactams

    Pedro Almendros

    2011-05-01

    Full Text Available New gold-catalyzed methods using the β-lactam scaffold have been recently developed for the synthesis of different sized heterocycles. This overview focuses on heterocyclization reactions of allenic and alkynic β-lactams which rely on the activation of the allene and alkyne component. The mechanism as well as the regio- and stereoselectivity of the cyclizations are also discussed.

  10. Self-association and infrared spectres of some heterocyclic compounds based on pyrrol in solid state

    Mulloev, N.; Nurulloev, M.; Narziev, B.N.

    1993-01-01

    Present article is devoted to self-association and infrared spectres of some heterocyclic compounds based on pyrrol in solid state. The study results of self-association specified by molecular hydrogen bonds of some heterocyclic compounds based on pyrrol on spectres of infrared absorption of stretching vibrations of N-H group were considered.

  11. Investigations on organogermanium compounds; III. N-tributylgermyl-substituted aliphatic and heterocyclic amines

    Rijkens, F.; Janssen, M.J.; Kerk, G.J.M. van der

    1965-01-01

    A series of new organogermanium compounds containing a germanium‐nitrogen bond, in many of which the nitrogen atom forms part of an heterocyclic ring, are prepared, in some cases by new methods: transamination reactions and reactions of germoxanes with heterocyclic amines. Striking differences in

  12. The GR-value deviation from the additivity rule for irradiated systems containing heterocyclic compounds

    Nanobashvili, H.M.; Shanidze, G.V.; Khidesheli, G.I.; Panchvidze, M.V.

    1988-01-01

    The investigation of the low temperature radiolysis of binary systems containing heterocyclic compounds has been carried out. In the systems under study the G R -value deviation from the additivity rule is observed due to the energy transfer processes from matrix molecules. It is shown that heterocyclic compounds are good radioprotectors. (author)

  13. Carbon-14 labelled nitrogen heterocycles; the syntheses of three phosphodiesterase inhibitors

    Lawrie, K.W.M.; Novelli, C.E.A.; Saunders, David

    1995-01-01

    The syntheses of three heterocyclic phosphodiesterase inhibitors are described from a common radiolabelled precursor, namely 2-propoxybenzo[cyano- 14 C] nitrile. Conversion of the nitrile to the corresponding methyl ketone or amidine allows elaboration of the heterocycles radiolabelled within the ring systems. (Author)

  14. Microwave-assisted synthesis of bio-active heterocycles in aqueous media

    Polshettiwar, Vivek

    2010-01-01

    Synthesis of bio-active heterocycles and fine chemicals in aqueous media are one of the best solutions for the development of green and sustainable protocols. To illustrate the advantages of aqueous MW chemistry in heterocycle synthesis, in this chapter, various synthetic pathways developed in recent years in aqueous reaction media using microwave irradiation are described.

  15. Carbon-14 labelled nitrogen heterocycles; the syntheses of three phosphodiesterase inhibitors

    Lawrie, K.W.M.; Novelli, C.E.A.; Saunders, David [SmithKline Beecham Pharmaceuticals Research and Development, Harlow (United Kingdom). Synthetic Isotope Chemistry Dept.; Coates, W.J. [SmithKline Beecham Pharmaceuticals Research and Development, Welwyn (United Kingdom)

    1995-09-01

    The syntheses of three heterocyclic phosphodiesterase inhibitors are described from a common radiolabelled precursor, namely 2-propoxybenzo[cyano-{sup 14}C] nitrile. Conversion of the nitrile to the corresponding methyl ketone or amidine allows elaboration of the heterocycles radiolabelled within the ring systems. (Author).

  16. An insight into the biological activities of heterocyclic-fatty acid hybrid molecules.

    Venepally, Vijayendar; Reddy Jala, Ram Chandra

    2017-12-01

    Heterocyclic compounds are the interesting core structures for the development of new bioactive compounds. Fatty acids are derived from renewable raw materials and exhibit various biological activities. Several researchers are amalgamating these two bioactive components to yield bioactive hybrid molecules with some desirable features. Heterocyclic-fatty acid hybrid derivatives are a new class of heterocyclic compounds with a broad range of biological activities and significance in the field of medicinal chemistry. Over the last few years, many research articles emphasized the significance of heterocyclic-fatty acid hybrid derivatives. The present review article focuses the developments in designing and biological evaluation of heterocyclic-fatty acid hybrid molecules. Copyright © 2017. Published by Elsevier Masson SAS.

  17. Synthesis of 2-arylidenebenzocycloalkanones containing N-donor heterocyclic rings

    Sun, S.-W., E-mail: sunsw0819@163.com [Yuncheng University, Department of Applied Chemistry (China); Zhang, X., E-mail: zhangx@hit.edu.cn [Harbin Institute of Technology, Academy of Fundamental and Interdisciplinary Science (China); Wang, G.-F. [Yuncheng University, Department of Applied Chemistry (China)

    2016-12-15

    A series of 2-arylidenebenzocycloalkanones containing heterocyclic rings 1–8 were prepared and characterized by IR, {sup 1}H NMR and elemental analyses. X-ray diffraction study of 6 reveals that the cyclohexyl ring of the 3,4-dihydronaphthalen-1(2H)-one adopts a chair conformation with a maximum deviation of 0.547(3) Å and makes dihedral angles of 52.24(17)° and 11.23(16)°, respectively, with the benzene plane and the mean plane of the benzimidazole ring.

  18. Condensed heterocycles with a thiazole ring. 13. Azinothiazoloquinoxalinium salts

    Nesterenko, Yu.A.; Romanov, N.N.

    1987-01-01

    The condensation of 2,3-dichloroquinoxaline with 2-mercaptopyridines and 2-mercaptoquinolines gave the corresponding derivatives of new heterocyclic systems, viz., azino[1',2':3,2]thaizolo[4,5-b]quinoxalinium salts, which can be used for the synthesis of cyanine dyes. The electronic spectra of solutions of the compounds were obtained with an SF-8 spectrophotometer. The PMR spectra of solutions of CF 3 COOD were recorded with a BS-467 spectrometer (60 MHz) with hexamethyldisiloxane (HMDS) as the external standard

  19. Solid-phase synthesis of complex and pharmacologically interesting heterocycles

    Nielsen, Thomas Eiland

    2009-01-01

    Efficient routes for the creation of heterocycles continue to be one of the primary goals for solid-phase synthesis. Recent advances in this field rely most notably on transition-metal-catalysis and N-acyliminium chemistry to mediate a range of cyclization processes for the generation of compounds...... with significant structural complexity and diversity. This review describes some of the most systematic solid-phase approaches that are potentially suited for pharmaceutical applications, that is, the methods described are useful for the synthesis of compound collections, and exhibit tunable stereochemistry...

  20. La piraterie sur le web

    2002-01-01

    Les échanges de toutes sortes sont facilités à l'extrême par le web: des forums, des vidéoconférences, le commerce à distance, ou tout simplement la célérité des courriers électroniques ou la convivialité des chats, tout cela participe de la société de communication. Une certaine partie du monde découvre le nouvel horizon des échanges quasi instantanés, mais... les transactions sur le web sont-elles vraiment s res?

  1. EKMEKLİK BUĞDAY ÇEŞİTLERİNDE FARKLI AZOT DOZLARININ BAZI VERİM ÖĞELERİ ÜZERİNE ETKİLERİ

    MERT, Berkan; ÇİFTÇİ, Cemalettin; ATAK, Mehmet

    2014-01-01

    Bu araştırma, 2002 yılında Ankara Üniversitesi, Ziraat Fakültesi Araştırma Uygulama Çiftliğinde yürütülmüştür. Araştırma, bazı ekmeklik buğday çeşitlerinde farklı azot dozlarının bazı verim öğeleri üzerine etkilerini incelemek amacıyla kurulmuştur. Denemede, Gün-91, İkizce-96, Mızrak, Uzunyayla ve Yakar-99 ekmeklik buğday çeşitleri materyal olarak kullanılmıştır. Beş değişik azot dozu (2, 4, 6, 8 ve 10 kg/da N) kullanılmış olup, azotun yarısı ekimle birlikte kalan diğer yarısı da sapa kalkma ...

  2. Synthesis of heterocyclic chalcone derivatives and their radical scavenging ability toward 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radicals

    Hwang, Kijun; Kim, Hoseok; Kim, Beomtae; Han, Incheol

    2012-01-01

    A series of heterocyclic chalcone derivatives bearing heterocycles such as thiophene or furan ring as an isostere of benzene ring were carefully prepared, and the influence of heterocycles on 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activities was systematically investigated. Structure-activity relationships (SAR) analysis showed that the activities of thiophene ring-containing chalcones were higher than those of furan ring containing chalcones, and the presence of methyl substituent of heterocyclic ring distinctly affected the activities compared with non-substituted heterocycles in an opposite manner, with the 4'-methyl group of thiophene ring increasing activity and the 3'-methyl group of the furan ring decreasing activity. The distinct isosteric effect of heterocycles (i.e., thiophene or furan ring) on radical scavenging activities of heterocyclic chalcones was distinctly demonstrated in our work

  3. Conductive Supramolecular Architecture Constructed from Polyoxovanadate Cluster and Heterocyclic Surfactant

    Toshiyuki Misawa

    2018-01-01

    Full Text Available Proton-conductive solid electrolytes are significant for fuel-cell battery technology. Especially for use in motor vehicles, proton conductors which work at intermediate temperatures (373–673 K under an anhydrous atmosphere are desired to improve the fuel cell stability and efficiency. Inorganic–organic hybrid supramolecular architectures are a promising option for the realization of highly conductive proton conductors. Here, a hybrid layered crystal was synthesized for the first time by using an proton-containing decavanadate (V10 anion and a heterocyclic surfactant cation. A simple ion-exchange reaction led to the formation of an inorganic–organic hybrid of V10 by using dodecylpyridazinium (C12pda as the heterocyclic surfactant. Single crystal X-ray analyses revealed that four C12pda cations were associated with one V10 anion, which was a diprotonated species forming a one-dimensional infinite chain structure through hydrogen bonds. Anhydrous proton conductivity was investigated by alternating current (AC impedance spectroscopy in the range of 313–393 K, exhibiting a maximum value of 1.7 × 10−5 S cm−1 at 373 K.

  4. Sorption of Heterocyclic Organic Compounds to Multiwalled Carbon Nanotubes.

    Metzelder, Florian; Funck, Matin; Schmidt, Torsten C

    2018-01-16

    Sorption is an important natural and technical process. Sorption coefficients are typically determined in batch experiments, but this may be challenging for weakly sorbing compounds. An alternative method enabling analysis of those compounds is column chromatography. A column packed with the sorbent is used and sorption data are determined by relating sorbate retention to that of a nonretarded tracer. In this study, column chromatography was applied for the first time to study sorption of previously hardly investigated heterocyclic organic compounds to multiwalled carbon nanotubes (MWCNTs). Sorption data for these compounds are very limited in literature, and weak sorption is expected from predictions. Deuterium oxide was used as nonretarded tracer. Sorption isotherms were well described by the Freundlich model and data showed reasonable agreement with predicted values. Sorption was exothermic and physisorption was observed. H-bonding may contribute to overall sorption, which is supported by reduced sorption with increasing ionic strength due to blocking of functional groups. Lowering pH reduced sorption of ionizable compounds, due to electrostatic repulsion at pH 3 where sorbent as well as sorbates were positively charged. Overall, column chromatography was successfully used to study sorption of heterocyclic compounds to MWCNTs and could be applied for other carbon-based sorbents.

  5. Thermally Stable Heterocyclic Imines as New Potential Nonlinear Optical Materials

    Nesterov, Volodymyr V.; Antipin, Mikhail Y.; Nesterov, Vladimir N.; Moore, Craig E.; Cardelino, Beatriz H.; Timofeeva, Tatiana V.

    2004-01-01

    In the course of a search for new thermostable acentric nonlinear optical crystalline materials, several heterocyclic imine derivatives were designed, with the general structure D-pi-A(D'). Introduction of a donor amino group (D') into the acceptor moiety was expected to bring H-bonds into their crystal structures, and so to elevate their melting points and assist in an acentric molecular packing. Six heterocycle-containing compounds of this type were prepared, single crystals were grown for five of them, and these crystals were characterized by X-ray analysis. A significant melting temperature elevation was found for all of the synthesized compounds. Three of the compounds were also found to crystallize in acentric space groups. One of the acentric compounds is built as a three-dimensional H-bonded molecular network. In the other two compounds, with very similar molecular structure, the molecules form one-dimensional H-bonded head-to-head associates (chains). These chains are parallel in two different crystallographic directions and form very unusual interpenetrating chain patterns in an acentric crystal. Two of the compounds crystallized with centrosymmetric molecular packing.

  6. Heterocyclic aramid nanoparticle-assisted graphene exfoliation for fabrication of pristine graphene-based composite paper

    Mo, Yao; Liu, Qi; Fan, Jinchen, E-mail: Jinchen.fan@shiep.edu.cn; Shi, Penghui; Min, Yulin, E-mail: ahaqmylin@126.com; Xu, Qunjie [Shanghai University of Electric Power, Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, College of Environmental and Chemical Engineering (China)

    2015-07-15

    Mechanically strong, electrically conductive, and flexible pristine graphene-based composite paper was prepared based on heterocyclic aramid nanoparticle-assisted liquid-phase exfoliation of graphite. The macroscopic heterocyclic aramid yarns were split and assembled into heterocyclic aramid nanoparticles with the size of ∼30 nm by deprotonation in dimethylsulfoxide in the presence of potassium hydroxide. The obtained heterocyclic aramid nanoparticles dimethylsulfoxide dispersion was used as good medium solvent for highly efficiency liquid-phase exfoliation of graphite. The results demonstrated that the concentration of exfoliated graphene can facile reaches ∼2.72 mg/mL after direct sonication of 7 h with assist of heterocyclic aramid nanoparticles. After exfoliation, the self-assembled pristine graphene-based composite paper was fabricated by vacuum-assisted filtration. Due to the introduction of heterocyclic aramid nanoparticles, the self-assembled pristine graphene/heterocyclic aramid nanoparticles composite paper exhibited good mechanical property with tensile strength of ∼129.7 MPa, meantime, has a high electrical conductivity of ∼1.42 × 10{sup 4} S/m.

  7. Heterocyclic aramid nanoparticle-assisted graphene exfoliation for fabrication of pristine graphene-based composite paper

    Mo, Yao; Liu, Qi; Fan, Jinchen; Shi, Penghui; Min, Yulin; Xu, Qunjie

    2015-01-01

    Mechanically strong, electrically conductive, and flexible pristine graphene-based composite paper was prepared based on heterocyclic aramid nanoparticle-assisted liquid-phase exfoliation of graphite. The macroscopic heterocyclic aramid yarns were split and assembled into heterocyclic aramid nanoparticles with the size of ∼30 nm by deprotonation in dimethylsulfoxide in the presence of potassium hydroxide. The obtained heterocyclic aramid nanoparticles dimethylsulfoxide dispersion was used as good medium solvent for highly efficiency liquid-phase exfoliation of graphite. The results demonstrated that the concentration of exfoliated graphene can facile reaches ∼2.72 mg/mL after direct sonication of 7 h with assist of heterocyclic aramid nanoparticles. After exfoliation, the self-assembled pristine graphene-based composite paper was fabricated by vacuum-assisted filtration. Due to the introduction of heterocyclic aramid nanoparticles, the self-assembled pristine graphene/heterocyclic aramid nanoparticles composite paper exhibited good mechanical property with tensile strength of ∼129.7 MPa, meantime, has a high electrical conductivity of ∼1.42 × 10 4  S/m.

  8. Effects of atmospheric fallouts of sulfur and nitrogen on soils and fresh waters in France; Effets des depots atmospheriques de soufre et d'azote sur les sols et les eaux douces en France

    Le Gall, A.Ch.

    2004-11-15

    The sulfur oxides, nitrogen oxides, the ammonia and the chlorine emitted in the environment by human activities contribute to the soils and waters acidity. After a presentation of the acidification and the eutrophication, the author describes and qualifies the mechanisms. In a second part she discusses the mathematical models of the acidification and the eutrophication, the biological criteria and the uncertainties. The last part presents the french situation and general recommendations on land restoration. (A.L.B.)

  9. Effects of ionization and nitrous oxide on grated carrot respiration; Effets de l`ionisation et du protoxyde d`azote sur la respiration de carottes rapees. Amelioration de la conservation de produits de 4eme gamme

    Chervin, C.

    1992-06-01

    Two treatments (nitrous oxide and irradiation) have been applied on grated carrots to reduce the respiratory crisis induced by wounding. Nitrous oxide inhibited cytochrome c oxidase; but, it neither diminished O{sub 2} consumption of the tissues, nor modified atmospheres in a favourable way for conservation of grated carrots, stored in plastic bags (in the conditions chosen for this study). On the contrary, irradiation inhibited simultaneously the respiratory crisis and the ethylene production, both induced by wounding. This behaviour led to a lower consumption of sugars in irradiated tissues and to the generation of atmospheres, which were better adapted to the conservation needs (it was necessary to use plastic film with high permeability). Finally, an applied study demonstrated that irradiation, by permitting a less denaturing preparation than industrial process, allowed the conservation of produces with a better quality (nutritional, sensory and microbiological). Biochemical analyses have been validated by sensory analyses.

  10. Effet de l'addition des tannins de châtaigniers sur la rétention azotée et la digestibilité chez les ruminants ingérant des produits herbagers

    Kriaa, S.

    1999-01-01

    Full Text Available The Influence of the Addition of Extract of Chestnut Tannin on the Nitrogen Balance and the Digestibility of Fresh Grass in Ruminant. The use of chestnut tannin (CT (hydrolysable Tannins, added at a low concentration (4 g CT/100 g of total nitrogen (TN = 0, 8 g cT/kg of DM distribute to a grass forage for growing sheep, improves the N retention (P <0, 01. The improvement of N retention is explained by the decrease of nitrogen in the urine, indicating a better use of absorbed nitrogen. Moreover, the addition at these low concentrations of CT to fresh grass does not alter neither the digestibility of its constituents (OM, TN, ADF nor the rate of ingestion.

  11. Effets d'enrichissements azotés sur la croissance des palourdes mises en élevage dans les claires du bassin de Marennes-Oléron

    Goulletquer, Philippe; Razet, Daniel; Prou, Jean; Garnier, Jacqueline; Taillade, Sylvie; Heral, Maurice; Peyre, R; Faivre, C

    1985-01-01

    Etant donné que la production de mollusques (palourdes ou huîtres) est limitée à 0,8 kg à 1 kg au m2 soit 40 à 50 palourdes adultes de 20 g au m2, il est intéressant d'essayer de forcer cette production en augmentant la production primaire qui est le facteur limitant de la production de palourdes. Cette production primaire dépend des apports en sels nutritifs en effet les travaux antérieurs de Zanette (1979), de Zanette et Garnier (1980), de Robert (1984) ont mis en évidence que les biomasses...

  12. Influence du type de fertilisation, du jour de pâturage et du mois de l'année sur les rejets azotés des vaches laitières

    Dufrasne I.

    2010-01-01

    Full Text Available Influence of the fertilization type, the day in the paddock and the month on nitrogen rejections in dairy cows. The present study aims to quantify nitrogen (N rejections in dairy cows on a rotational grazing system with different types of fertilization (compost, slurry and mineral N at two different days in the paddock (days 3 and 5 and during two different periods (June and September. Grass yield and height were measured along with the chemical composition. The live weight was recorded when the cows moved into the paddock and milk yields was recorded at each milking. N intakes were measured on the basis of the energy requirement. When the cows were in the paddocks, individual samples of faeces and urine were collected to assess N rejections. The urea content in milk from the tank or from the individual cows was also measured. N intake was higher on day 3 than on day 5 and in September as compared with in June but was not influenced by the fertilization. The amount of N produced in milk was not influenced either by the fertilization, by the day on the paddock or by the month. The amount of urinary N was significantly higher in the N mineral group than in the two other groups. The N excretion in faeces and urines was higher on day 3 than on day 5. In June, the N excretion by the urine was lower than in September while the N excretion by the faeces was higher. Equations were calculated in order to estimate the N excretion by the urine in grazing dairy cows from the urea content in milk of a group of cows.

  13. Antiradiation compounds XV: condensations of carbon disulfide with amino, chloro, cyanomethyl, and sulfonamido heterocycles

    Foye, W.O.; Kauffman, J.M.; Lanzillo, J.J.; LaSala, E.F.

    1975-01-01

    Condensations of carbon disulfide were carried out with amino, chloro, and diamino heterocycles to give condensed ring thiazoline-2-thiones and imidazoline-2-thiones, with cyanomethyl heterocycles to give dithio acid derivatives, and with heterocyclic sulfonamides to give sulfonyldithiocarbamates. Of several examples tested, pyrido[3,2-d]thiazoline-2-thione, disodium 2-(5-chloro-2-thienyl)-3,3-dimercaptoacrylonitrile, triethylammonium 4-sulfamoylphenyldithiocarbamate, ammonium β-phenethyldithiocarbamate, and methyl N-(thiophene-2-sulfonyl)dithiocarbamate, only the last-named compound showed any radiation protection for mice. Several compounds gave negative tests for antimalarial activity

  14. Influence des matières végétales et des engrais NPK sur la biologie de Aedes aegypti (Diptera : Culicidae

    Darriet F.

    2010-06-01

    Full Text Available Dans cette étude de laboratoire, les auteurs ont mesuré sur des femelles gravides de Aedes aegypti, l’attractivité à la ponte de milieux aqueux contenant un engrais NPK, de la matière végétale (MV et un mélange composé de MV+NPK. Tandis que les analyses physico-chimiques ont permis d’identifier puis de doser les constituants de chaque milieu, le suivi des larves et la pesée des femelles émergentes nous ont renseigné sur l’impact des composés minéraux et organiques sur le développement des moustiques. Sur les 23 jours qu’a duré l’expérience, la solution NPK est restée aussi attractive que le mélange MV+NPK sans toutefois pouvoir assurer le développement des larves. L’infusion MV a révélé une attractivité à la ponte moins importante, mais elle a apporté aux larves de moustiques les substances organiques dont la solution NPK était dépourvue. Enfin le mélange MV+NPK a attiré les femelles à la ponte tout en assurant pleinement la croissance des larves de Ae. aegypti. Alors que les analyses physico-chimiques de NPK ont révélé une composition essentiellement minérale (NH4++NO3–+P+K et celles de MV de fortes concentrations en carbone et en azote organiques, le mélange MV+NPK s’est distingué par une composition mixte organique et minérale qui a favorisé la prolifération des bactéries et le développement des larves de moustiques. Ce sont des observations importantes qui pourraient aider à la fabrication de pièges à la fois attractifs et létaux (NPK+larvicide et dont les fonctions seraient de piéger les femelles gravides à la recherche d’un lieu de ponte et de tuer les larves à l’éclosion des oeufs.

  15. Sur des erres de jazz

    Daverat, Xavier

    2007-01-01

    Une opinion commune considère que le jazz vivrait une période de dépérissement ou de ressassement. Cette conception est d’abord basée sur une erreur qui consiste à croire que le jazz évolue uniquement au travers de relèves entre les générations, de substitutions complètes de nouveaux styles à des formes d’expression qui se démoderaient aussitôt, d’instaurations systématiques de nouveaux langages opposés à ceux qui les ont précédés. Au contraire, les caractéristiques de chaque style s’imbrique...

  16. Heterocyclic N-oxides - A Promising Class of Agents Against Tuberculosis, Malaria and Neglected Tropical Diseases.

    Dos Santos Fernandes, Guilherme Felipe; Pavan, Aline Renata; Dos Santos, Jean Leandro

    2018-04-17

    Heterocyclic N-oxides have emerged as promising agents against a number of diseases and disorders, especially infectious diseases. This review analyzes the emergence and development of this scaffold in the medicinal chemistry, focusing mainly on the discovery of new heterocyclic N-oxide compounds with potent activity against tuberculosis, malaria and neglected tropical diseases (i.e. leishmaniasis and Chagas disease). A number of heterocyclic N-oxide are described herein, nevertheless, the following chemical classes deserve to be highlighted due to the large number of reports in the literature about their promising pharmacological effects: furoxan, benzofuroxan, quinoxaline 1,4-di-N-oxide, indolone N-oxide and benzimidazole N-oxide. In order to describe those most promising compounds, we included in this review only those most biologically active heterocyclic N-oxide published since 2000. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  17. Adsorption Characteristics of DNA Nucleobases, Aromatic Amino Acids and Heterocyclic Molecules on Silicene and Germanene Monolayers

    Hussain, Tanveer; Vovusha, Hakkim; Kaewmaraya, Thanayut; Amornkitbamrung, Vittaya; Ahuja, Rajeev

    2017-01-01

    Binding of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules on two-dimensional silicene and germanene sheets have been investigated for the application of sensing of biomolecules using first principle density functional theory

  18. Sulfur-Kβ /sub emission studies on sulfur-bearing heterocycles

    Phillips, D.R.; Andermann, G.G.; Fujiwara, F.

    1986-01-01

    Sulfur-K/β /sub x-ray fluorescence spectroscopy (XFS) has been used to study the electronic structure and bonding in sulfur-bearing heterocycles. XFS not only has the capability of experimentally measuring valence electron energies in molecular species, but can also provide intensity data which can help define the nature of the molecular orbitals defined by the electrons. This report discusses the feasibility of using XFS as an analytical tool for the determination of total and specific sulfur heterocycle content in samples. A variety of compounds were studied. These include thiophene, thiophene derivatives, tetranydrothiophene, several more complex saturated and unsaturated sulfur heterocycles, and heterocycles containing both sulfur and nitrogen. The sulfur-K/β /sub spectra were obtained using a double crystal spectrometer which provided an instrumental resolution of about 0.7 eV

  19. Synthesis and properties of nitrogenous heterocycles containing a spiro-fused cyclopropane fragment

    Tomilov, Yury V; Nefedov, Oleg M; Kostyuchenko, Irina V

    2000-01-01

    The published data on the methods of synthesis and chemical transformations of nitrogenous heterocyclic compounds spiro-fused with a cyclopropane fragment are described systematically and generalised. The bibliography includes 146 references.

  20. Synthesis of heterocyclic compounds through palladium-catalyzed C-H cyclization processes.

    Inamoto, Kiyofumi

    2013-01-01

    Herein, we describe our development of synthetic methods for heterocyclic compounds based on the palladium-catalyzed carbon-hydrogen bond (C-H) functionalization/intramolecular carbon-heteroatom (nitrogen or sulfur) bond formation process. By this C-H cyclization method, we efficiently prepared various N-heterocycles, including indazoles, indoles, and 2-quinolinones, as well as S-heterocycles such as benzothiazoles and benzo[b]thiophenes. Yields are typically good to high and good functional-group tolerance is observed for each process, thereby indicating that the method provides a novel, highly applicable synthetic route to the abovementioned biologically important heterocyclic frameworks. As an application of this approach, an auto-tandem-type, one-pot process involving the oxidative Heck reaction and subsequent C-H cyclization using cinnamamides and arylboronic acids as starting materials in the presence of a palladium catalyst was also developed for the rapid construction of the 2-quinolinone nucleus.

  1. Recyclisation of carbo- and heterocyclic compounds involving malononitrile and its derivatives

    Litvinov, Victor P

    1999-01-01

    Published data on recyclisation reactions of carbo- and heterocycles with participation of malononitrile and recyclisation of compounds containing a malononitrile fragment or fragments with malononitrile as a synthon are surveyed, described systematically and analysed. The bibliography includes 206 references.

  2. Physicochemical Mechanisms of Synergistic Biological Action of Combinations of Aromatic Heterocyclic Compounds

    Evstigneev, Maxim P.

    2013-01-01

    The mechanisms of synergistic biological effects observed in the simultaneous use of aromatic heterocyclic compounds in combination are reviewed, and the specific biological role of heteroassociation of aromatic molecules is discussed.

  3. Microwave-Assisted Synthesis of Bio-Active Heterocycles and Fine Chemicals in Aqueous Media

    Human health, especially in the aging population, mostly depends on various medicines, and researchers are combating against emerging diseases by new drug discovery. Heterocyclic compounds hold a special place among pharmaceutically active natural products as well as synthetic co...

  4. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    Falivene, Laura; Cavallo, Luigi

    2016-01-01

    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise

  5. Studies of effect of heterocyclic dyes in photogalvanic cells for solar ...

    Unknown

    Studies of effect of heterocyclic dyes in photogalvanic cells for solar ... observed and current–voltage characteristics of the cell studied, and a mechanism has been proposed for the generation ... dye work effectively in the strong alkaline range.

  6. Basic nitrogen-heterocyclic compounds in the Murchison meteorite

    Stoks, P.G.; Schwartz, A.W.

    1982-01-01

    A fragment of the Murchison (C2) carbonaceous meteorite was analyzed for basic, N-heterocyclic compounds, by dual detector capillary gas chromatography as well as capillary gas chromatography/mass spectrometry, using two columns of different polarity. In the formic acid extract 2,4,6-trimethylpyridine, quinoline, isoquinoline, 2-methylquinoline and 4-methylquinoline were positively identified. In addition, a suite of alkylpyridines and quinolines and/or isoquinolines was tentatively identified from their mass spectra. The (iso)quinolines were found to contain methyl substituents exclusively. The distribution of the pyridines observed reveals a similarity to that observed from catalytic reactions of ammonia and simple aldehydes under conditions similar to those applied in Fischer-Tropsch type reactions. (author)

  7. Vapor pressures and sublimation enthalpies of novel bicyclic heterocycle derivatives

    Blokhina, Svetlana V.; Ol’khovich, Marina V.; Sharapova, Angelica V.; Perlovich, German L.; Proshin, Alexey N.

    2014-01-01

    Highlights: • The vapor pressures of novel bicyclo-derivatives of amine were measured. • Thermodynamic functions of sublimation were calculated. • The influence of substituent structure and chemical nature on the vapor pressure was studied. -- Abstract: The vapor pressures of five novel bicyclic heterocycle derivatives were measured over the temperature 341.15 to 396.15 K using the transpiration method by means of an inert gas carrier. From these results the standard enthalpies and Gibbs free energies of sublimation at the temperature 298.15 K were calculated. The effects of alkyl- and chloro-substitutions on changes in the thermodynamic functions have been investigated. Quantitative structure–property relationship on the basis HYBOT physico-chemical descriptors for biologically active compounds have been developed to predict the sublimation enthalpies and Gibbs free energies of the compounds studied

  8. Alkyne hydroarylation with Au N-heterocyclic carbene catalysts

    Cristina Tubaro

    2013-02-01

    Full Text Available Mono- and dinuclear gold complexes with N-heterocyclic carbene (NHC ligands have been employed as catalysts in the intermolecular hydroarylation of alkynes with simple unfunctionalised arenes. Both mono- and dinuclear gold(III complexes were able to catalyze the reaction; however, the best results were obtained with the mononuclear gold(I complex IPrAuCl. This complex, activated with one equivalent of silver tetrafluoroborate, exhibited under acidic conditions at room temperature much higher catalytic activity and selectivity compared to more commonly employed palladium(II catalysts. Moreover, the complex was active, albeit to a minor extent, even under neutral conditions, and exhibited lower activity but higher selectivity compared to the previously published complex AuCl(PPh3. Preliminary results on intramolecular hydroarylations using this catalytic system indicate, however, that alkyne hydration by traces of water may become a serious competing reaction.

  9. Synthesis of heterocycle-attached methylidenebenzenesulfonohydrazones as antifungal agents.

    Gao, Zhinan; Lv, Min; Li, Qin; Xu, Hui

    2015-11-15

    A series of heterocycle-attached methylidenebenzenesulfonohydrazone derivatives were synthesized and evaluated for their antifungal activities against seven phytopathogenic fungi such as Fusarium graminearum, Alternaria solani, Valsa mali, Phytophthora capsici, Fusarium solani, Botrytis cinerea, and Glomerella cingulata. Compounds 7b, 8d, 9a, 9b and 9d exhibited a good and broad-spectrum of antifungal activities against at least five phytopathogenic fungi at the concentration of 100 μg/mL. It demonstrated that addition of one double bond between the phenylsulfonylhydrazone fragment and the furan ring of 6a,b,d could afford more active compounds 9a,b,d; however, introduction of the nitro group on the phenyl ring of 6a-9a gave less potent compounds 6e-9e. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Radical fragmentation of six-membered oxygen-containing heterocycles

    Petryaev, E.P.; Kosobutskij, V.S.; Shadyro, O.I.

    1982-01-01

    Using chromatography, the composition and radiation-chemical yields of final products of desctruction of six-member saturated oxygen-containing heterocycles (the effect of #betta#-radiation on aqueous solutions of tetrahydropyran, 1,3-dioxane, 2,2 dimethyl-1,3 dioxane, 1,4-dioxane, paraldehyde) have been determined. It is established that the identified products are formed at the expense of decomposition of primary radicals of the initial compounds and point to the realization of the following fragmentation ways: 1) #betta#-scattering, 2) #betta#-scattering with a subsequent 1,5 migration of an H atom, 3) simultaneous rupture of two vicinal, relative to the radical center, bonds. A formation mechanism of the substances desctruction products is suggested. Material balance of the product yields of 1,3-dioxane radical synchronous decomposition is presented

  11. Radical Addition to Iminium Ions and Cationic Heterocycles

    Johannes Tauber

    2014-10-01

    Full Text Available Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta reaction, and the Knabe rearrangement will be discussed along with transition metal and photoredox catalysis or electrochemical methods to generate the odd-electron species.

  12. α-Diazo oxime ethers for N-heterocycle synthesis.

    Choi, Subin; Ha, Sujin; Park, Cheol-Min

    2017-06-01

    This Feature Article introduces the preparation and synthetic utility of α-diazo oxime ethers. α-Oximino carbenes are useful synthons for N-heterocycles, and can be easily prepared from α-diazo oxime ethers as precursors. We begin with the preparation of α-diazo oxime ethers and their application in [3+2] cycloaddition. It turns out that the nature of metals bound to carbenes plays a crucial role in modulating the reactivity of α-oximino carbenes, in which copper carbenes smoothly react with enamines, whereas the less reactive enol ethers and nitriles require gold carbenes. In Section 3.2, a discussion on N-O and C-H bond activation is presented. Carbenes derived from diazo oxime ethers show unique reactivity towards N-O and C-H bond activation, in which the proximity of the two functionalities, carbene and oxime ether, dictates the preferred reaction pathways toward pyridines, pyrroles, and 2H-azirines. In Section 3.3, the development of tandem reactions based on α-diazo oxime ethers is discussed. The nature of carbenes in which whether free carbenes or metal complexes are involved dissects the pathway and forms different types of 2H-azirines. The 2H-azirine formation turned out to be an excellent platform for the tandem synthesis of N-heterocycles including pyrroles and pyridines. In the last section, we describe the electrophilic activation of 2H-azirines with vinyl carbenes and oximino carbenes. The resulting azirinium species undergo rapid ring expansion rearrangements to form pyridines and pyrazines.

  13. Selective Access to Heterocyclic Sulfonamides and Sulfonyl Fluorides via a Parallel Medicinal Chemistry Enabled Method.

    Tucker, Joseph W; Chenard, Lois; Young, Joseph M

    2015-11-09

    A sulfur-functionalized aminoacrolein derivative is used for the efficient and selective synthesis of heterocyclic sulfonyl chlorides, sulfonyl fluorides, and sulfonamides. The development of a 3-step parallel medicinal chemistry (PMC) protocol for the synthesis of pyrazole-4-sulfonamides effectively demonstrates the utility of this reagent. This reactivity was expanded to provide rapid access to other heterocyclic sulfonyl fluorides, including pyrimidines and pyridines, whose corresponding sulfonyl chlorides lack suitable chemical stability.

  14. Phosphorylated Derivatives of Alkaloids and Nitrogen-containing Heterocycles — Cholinesterase Inhibitors

    Sadykov, Abid S.; Dalimov, D. N.; Godovikov, Nikolai N.

    1983-10-01

    The review deals with the synthesis and anticholinesterase activities of phosphorylated derivatives of certain alkaloids and nitrogen-containing heterocycles. It is shown that the conformational properties of the alkaloid and nitrogen-containing heterocycle residues in the composition of the organophosphorus inhibitor (OPI) molecule play an important role in the inhibition of the catalytic activity of cholinesterases. The type of inhibition of cholinesterases also varies as a function of chemical structure. The bibliography includes 45 references.

  15. Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds: Synthetic Routes, Properties, and Applications.

    Stępień, Marcin; Gońka, Elżbieta; Żyła, Marika; Sprutta, Natasza

    2017-02-22

    Two-dimensionally extended, polycyclic heteroaromatic molecules (heterocyclic nanographenes) are a highly versatile class of organic materials, applicable as functional chromophores and organic semiconductors. In this Review, we discuss the rich chemistry of large heteroaromatics, focusing on their synthesis, electronic properties, and applications in materials science. This Review summarizes the historical development and current state of the art in this rapidly expanding field of research, which has become one of the key exploration areas of modern heterocyclic chemistry.

  16. Synthesis and antiacetylcholinesterase activity of new D-glyceraldehyde heterocyclic derivatives

    Scorzo, Cecilia M.; Fascio, Mirta L.; D' Accorso, Norma B. [Universidad de Buenos Aires, Buenos Aires (Argentina). Facultad de Ciencias Exactas y Naturales. Dept. de Quimica Organica; Cabrera, Margarita Gutierrez; Saavedra, Luis Astudillo [Universidad de Talca (Chile). Inst. de Quimica de Productos Naturales. Lab. de Sintesis Organica

    2010-07-01

    We report herein the convenient procedures for the syntheses of different heterocyclic compounds from 2,3-O-isopropylidene-D-glyceraldehyde using intramolecular cyclization, 1,3-dipolar cycloaddition or bimolecular coupling reactions. The products were characterized by {sup 1}H and {sup 13}C NMR spectroscopy and elemental analysis. The new heterocycles and their derivatives were evaluated as inhibitors of acetylcholinesterase enzyme. (author)

  17. An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals

    Nikzad Nikbin

    2011-04-01

    Full Text Available This review presents a comprehensive overview on selected synthetic routes towards commercial drug compounds as published in both journal and patent literature. Owing to the vast number of potential structures, we have concentrated only on those drugs containing five-membered heterocycles and focused principally on the assembly of the heterocyclic core. In order to target the most representative chemical entities the examples discussed have been selected from the top 200 best selling drugs of recent years.

  18. [Distribution and sources of oxygen and sulfur heterocyclic aromatic compounds in surface soil of Beijing, China].

    He, Guang-Xiu; Zhang, Zhi-Huan; Peng, Xu-Yang; Zhu, Lei; Lu, Ling

    2011-11-01

    62 surface soil samples were collected from different environmental function zones in Beijing. Sulfur and oxygen heterocyclic aromatic compounds were detected by GC/MS. The objectives of this study were to identify the composition and distribution of these compounds, and discuss their sources. The results showed that the oxygen and sulfur heterocyclic aromatic compounds in the surface soils mainly contained dibenzofuran, methyl- and C2-dibenzofuran series, dibenzothiophene, methyl-, C2- and C3-dibenzothiophene series and benzonaphthothiophene series. The composition and distribution of the oxygen and sulfur heterocyclic aromatic compounds in the surface soil samples varied in the different environmental function zones, of which some factories and the urban area received oxygen and sulfur heterocyclic aromatic compounds most seriously. In Beijing, the degree of contamination by oxygen and sulfur heterocyclic aromatic compounds in the north surface soil was higher than that in the south. There were preferable linear correlations between the concentration of dibenzofuran series and fluorene series, as well as the concentration of dibenzothiophene series and dibenzofuran series. The oxygen and sulfur heterocyclic aromatic compounds in the surface soil were mainly derived from combustion products of oil and coal and direct input of mineral oil, etc. There were some variations in pollution sources of different environmental function zones.

  19. Experiments with the SUR 100 training reactor

    Milicic, B.

    1984-06-01

    This paper contains a compilation of various experiments using the SUR - 100 reactor for training purposes, which have been widly proved in practical work at the School for Nuclear Technology of the Karlsruhe Research Center. (orig.) [de

  20. Delayed neutron detection in canning burst detection studies (1961); Etude sur la detection des neutrons differes en vue de la detection des ruptures de gaines (1961)

    Perlini, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    This paper describes a theoretical and experimental study on the detection of neutrons present in the primary cooling circuit of a reactor cooled by heavy or light water, with a view to the installation of a canning burst detection unit. The concentration of background neutrons is first calculated, taking into account the neutrons from nitrogen 17 decay, and the photoneutrons produced by the decay of nitrogen 16 and sodium 24. The emission of delayed fission neutrons, originating at a given crack in the canning, has been estimated. Using the D{sub 2}O circuit of the pile EL-3, three units have been developed by means of which the following three types of detector may be compared: 1) BF{sub 3} proportional counter 2) Boron scintillator 3) Fission chamber Under the present experimental conditions the BF{sub 3} counter gave the best results. The influence on these detectors of the {gamma} flux, which in certain cases reaches 200 R/h, is analysed. Finally a calibration is carried out with an experimental crack of 30 mm{sup 2} of uranium exposed to a flux of 5.8 x 10{sup 13} n.cm{sup -2}.s{sup -1}. The sensitivity obtained with the BF{sub 3} counter during this test is 2 counts/s per mm{sup 2} of exposed uranium. (author) [French] Le present rapport est une etude theorique et experimentale sur la detection des neutrons presents dans le circuit primaire de refroidissement d'un reacteur refrigere par l'eau lourde ou l'eau legere, en vue d'une installation de detection de ruptures de gaines. On fait d'abord un calcul sur la concentration des neutrons de bruit de fond en tenant compte: des neutrons de decroissance de l'azote 17 et des photoneutrons produits par les decroissances de l'azote 16 et du sodium 24. L'emission des neutrons differes de fission, qui ont pour origine une fissure de gaine donnee, a ete evaluee. Utilisant le circuit D{sub 2}O de la pile EL3, trois installations ont ete mises au point permettant de comparer les trois types de detecteurs suivants: 1

  1. Dietary exposure to heterocyclic amines in high-temperature cooked meat and fish in Malaysia.

    Jahurul, M H A; Jinap, S; Ang, S J; Abdul-Hamid, A; Hajeb, P; Lioe, H N; Zaidul, I S M

    2010-08-01

    The intake of heterocyclic amines is influenced by the amount and type of meat and fish ingested, frequency of consumption, cooking methods, cooking temperature, and duration of cooking. In this study, the dietary intake of heterocyclic amines in Malaysia and their main sources were investigated. Forty-two samples of meat and fish were analysed by high-performance liquid chromatography with photodiode array detector to determine the concentration of the six predominant heterocyclic amines, namely: 2-amino-3-methylimidazo[4,5-f] quinoline (IQ), 2-amino-3,4-dimethylimidazo[4,5-f] quinoline(MeIQ), 2-amino-3,8-dimethylimidazo[4,5-f] quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f] quinoxaline (4,8-DiMeIQx), 2-amino-3,7,8-trimethylimidazo[4,5-f] quinoxaline (7,8-DiMeIQx), and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP). Dietary intake data were obtained using a food-frequency questionnaire when interviewing 600 Malaysian respondents. The level of total heterocyclic amines in food samples studies ranged from not detected to 38.7 ng g(-1). The average daily intake level of heterocyclic amine was 553.7 ng per capita day(-1). The intake of PhIP was the highest, followed by MeIQx and MeIQ. The results reveal that fried and grilled chicken were the major dietary source of heterocyclic amines in Malaysia. However, the heterocyclic amine intake by the Malaysian population was lower than those reported from other regions.

  2. Componentes voláteis do café torrado. Parte I: compostos heterocíclicos Volatile components in roasted coffee. Part I: heterocyclic compounds

    Carlos Alberto Bastos De Maria

    1999-04-01

    Full Text Available A review of heterocyclic compounds in roasted coffee is presented. The contents, precursors and sensorial properties of furans, pyrroles, oxazoles, thiazoles, thiophenes, pyrazines and pyridines are discussed. The impact heterocyclic compounds of coffee aroma are described.

  3. Pockmarks off Big Sur, California

    Paull, C.; Ussler, W.; Maher, N.; Greene, H. Gary; Rehder, G.; Lorenson, T.; Lee, H.

    2002-01-01

    A pockmark field was discovered during EM-300 multi-beam bathymetric surveys on the lower continental slope off the Big Sur coast of California. The field contains ??? 1500 pockmarks which are between 130 and 260 m in diameter, and typically are 8-12 m deep located within a 560 km2 area. To investigate the origin of these features, piston cores were collected from both the interior and the flanks of the pockmarks, and remotely operated vehicle observation (ROV) video and sampling transects were conducted which passed through 19 of the pockmarks. The water column within and above the pockmarks was sampled for methane concentration. Piston cores and ROV collected push cores show that the pockmark field is composed of monotonous fine silts and clays and the cores within the pockmarks are indistinguishable from those outside the pockmarks. No evidence for either sediment winnowing or diagenetic alteration suggestive of fluid venting was obtained. 14C measurements of the organic carbon in the sediments indicate continuous sedimentation throughout the time resolution of the radiocarbon technique ( ??? 45000 yr BP), with a sedimentation rate of ??? 10 cm per 1000 yr both within and between the pockmarks. Concentrations of methane, dissolved inorganic carbon, sulfate, chloride, and ammonium in pore water extracted from within the cores are generally similar in composition to seawater and show little change with depth, suggesting low biogeochemical activity. These pore water chemical gradients indicate that neither significant accumulations of gas are likely to exist in the shallow subsurface ( ??? 100 m) nor is active fluid advection occurring within the sampled sediments. Taken together the data indicate that these pockmarks are more than 45000 yr old, are presently inactive, and contain no indications of earlier fluid or gas venting events. ?? 2002 Elsevier Science B.V. All rights reserved.

  4. Synthesis and Biological Activity Evaluation of Novel Heterocyclic Pleuromutilin Derivatives

    Yunpeng Yi

    2017-06-01

    Full Text Available A series of pleuromutilin derivatives were synthesized by two synthetic procedures under mild reaction conditions and characterized by Nuclear Magnetic Resonance (NMR, Infrared Spectroscopy (IR, and High Resolution Mass Spectrometer (HRMS. Most of the derivatives with heterocyclic groups at the C-14 side of pleuromutilin exhibited excellent in vitro antibacterial activities against Staphylococcus aureus, methicillin-resistant Staphylococcus aureus (MRSA, methicillin-resistant Staphylococcus epidermidis (MRSE, and vancomycin-resistant Enterococcus (VRE in vitro antibacterial activity. The synthesized derivatives which contained pyrimidine rings, 3a, 3b, and 3f, displayed modest antibacterial activities. Compound 3a, the most active antibacterial agent, displayed rapid bactericidal activity and affected bacterial growth in the same manner as that of tiamulin fumarate. Moreover, molecular docking studies of 3a and lefamulin provided similar information about the interactions between the compounds and 50S ribosomal subunit. The results of the study show that pyrimidine rings should be considered in the drug design of pleuromutilin derivatives.

  5. The Effect of Novel Heterocyclic Compounds on Cryptococcal Biofilm

    Korem, Maya; Kagan, Sarah

    2017-01-01

    Biofilm formation by microorganisms depends on their communication by quorum sensing, which is mediated by small diffusible signaling molecules that accumulate in the extracellular environment. During human infection, the pathogenic yeast Cryptococcus neoformans can form biofilm on medical devices, which protects the organism and increases its resistance to antifungal agents. The aim of this study was to test two novel heterocyclic compounds, S-8 (thiazolidinedione derivative, TZD) and NA-8 (succinimide derivative, SI), for their anti-biofilm activity against strains of Cryptococcus neoformans and Cryptococcus gattii. Biofilms were formed in a defined medium in 96-well polystyrene plates and 8-well micro-slides. The effect of sub-inhibitory concentrations of S-8 and NA-8 on biofilm formation was measured after 48 h by a metabolic reduction assay and by confocal laser microscopy analysis using fluorescent staining. The formation and development of cryptococcal biofilms was inhibited significantly by these compounds in concentrations below the minimum inhibitory concentration (MIC) values. These compounds may have a potential role in preventing fungal biofilm development on indwelling medical devices or even as a therapeutic measure after the establishment of biofilm. PMID:29371559

  6. Immobilization of N-Heterocyclic Carbene Compounds: A Synthetic Perspective.

    Zhong, Rui; Lindhorst, Anja C; Groche, Florian J; Kühn, Fritz E

    2017-02-08

    Over the course of the past 15 years the success story of N-heterocyclic carbene (NHC) compounds in organic, inorganic, and organometallic chemistry has been extended to another dimension. The immobilization of NHC compounds, undergoing continuous diversification, broadens their range of applications and leads to new solutions for challenges in catalytic and synthetic chemistry. This review intends to present a synthetic toolkit for the immobilization of NHC compounds, giving the reader an overview on synthetic techniques and strategies available in the literature. By individually summarizing and assessing the synthetic steps of the immobilization process, a comprehensive picture of the strategies and methodologies for the immobilization of NHC compounds is presented. Furthermore, the characterization of supported NHC compounds is discussed in detail in order to set up necessary criteria for an in-depth analysis of the immobilized derivatives. Finally, the catalytic applications of immobilized NHC compounds are briefly reviewed to illustrate the practical use of this technique for a broad variety of reaction types.

  7. Selected heterocyclic compounds as antioxidants. Synthesis and biological evaluation.

    Tsolaki, E; Nobelos, P; Geronikaki, A; Rekka, E A

    2014-01-01

    Reactive oxygen species, oxidative stress, and oxidative damage are increasingly assigned important roles as harmful factors in pathological conditions and ageing. ROS are potentially reactive molecules derived from the reduction of molecular oxygen in the course of aerobic metabolism. ROS can also be produced through a variety of enzymes. Under normal circumstances, ROS concentrations are tightly controlled by physiological antioxidants. When excessively produced, or when antioxidants are depleted, ROS can impose oxidative damage to lipids, proteins, sugars and DNA. This reduction-oxidation imbalance, called oxidative stress, can subsequently contribute to the development and progression of tissue damage and play a role in the pathology of various diseases. An antioxidant is defined as "any substance that, when present at low concentrations compared with those of a substrate, significantly delays, prevents or removes oxidative damage to this target molecule". Despite evidence that oxidative damage contributes to a wide range of clinically important conditions, few antioxidants act as effective drugs in vivo. Inter alia, the difficulty of measuring antioxidant efficacy in vivo makes the interpretation of results from clinical trials difficult. A large number of synthetic compounds have been reported to possess antioxidant activity. Several of them derive from natural antioxidants, others have various structures. In this review, some of the most often reported classes of heterocyclic antioxidant compounds, as well as methods for evaluation of their antioxidant activity are discussed.

  8. Occurrence of heterocyclic amines in cooked meat products.

    Puangsombat, Kanithaporn; Gadgil, Priyadarshini; Houser, Terry A; Hunt, Melvin C; Smith, J Scott

    2012-03-01

    Heterocyclic amines (HCAs), potent mutagens and a risk factor for human cancers, are produced in meats cooked at high temperature. The aim of this study was to determine the HCA content in cooked meat products (beef, chicken, pork, fish) prepared by various cooking methods (pan frying, oven broiling, and oven baking at 170 to 230°C) that are preferred by U.S. meat consumers. The primary HCAs in these samples were PhIP (2-amino-1-methyl-6-phenylimidazo [4,5-b]pyridine) (1.49-10.89ng/g), MeIQx (2-amino-3,8-dimethylimidazo [4,5-f]quinoxaline) (not detected-4.0ng/g), and DiMeIQx (2-amino-3,4,8-trimethyl-imidazo [4,5-f]quinoxaline) (not detected-3.57ng/g). Type and content of HCAs in cooked meat samples were highly dependent on cooking conditions. The total HCA content in well-done meat was 3.5 times higher than that of medium-rare meat. Fried pork (13.91ng/g) had higher levels of total HCAs than fried beef (8.92ng/g) and fried chicken (7.00ng/g). Among the samples, fried bacon contained the highest total HCA content (17.59ng/g). Copyright © 2011 Elsevier Ltd. All rights reserved.

  9. On the radioprotective properties of heterocyclic nitrogenous compounds

    Rinaldi, R.; Bernard, Y.

    1964-01-01

    Continuing their study of the possible radioprotective properties of heterocyclic nitrogenous compounds, the authors study certain derivatives of imidazole and other compounds of similar structure. The results obtained showed: 1 - that the derivatives resulting from the presence in the imidazole ring of the mercapto, methyl, carbonyl, or benzyl groups are inactive: these substitutions appear to destroy the significant radioprotective activity of the imidazole, 2 - that benzimidazole, on the contrary, seems to possess highly interesting properties. The percentage of survivals obtained with mice treated with benzimidazole and exposed to lethal irradiation has encouraged the authors to undertake careful study of this substance, with a view to define optimum activity conditions, and to determine the mechanism responsible for its radioprotective action. Further on and so as to of clarify certain points that might give useful data concerning the mechanisms of action of radioprotective chemicals, in respect of each of the products the authors have studied: a - the action of these bodies on the internal temperature of mice, b - their radioprotective activity in vitro, in a solution of irradiated hemin. (authors) [fr

  10. Purification by molecular sieve of helium used as inert cover gas in nuclear reactors; Epuration de l'helium de couverture des reacteurs nucleaires par adsorption sur tamis moleculaire

    Rozenberg, J; Kahan, H [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-07-01

    A method carried out at fairly low temperatures (between -50 and -80 deg. C) has been studied for the purification of the helium used as cover gas for heavy water in reactors. The use of the 5A molecular sieve has been adopted because of its superiority over other adsorbents in this temperature range. The particular problems connected with adsorption under dynamic conditions have been dealt with separately. The nitrogen adsorption isotherms have been plotted and the heat of adsorption calculated. (authors) [French] Une methode d'epuration, a temperature moderement basse (comprise entre -50 et -80 deg. C) de l'helium servant de couverture inerte a l'eau lourde des reacteurs a ete etudiee. L'emploi au tamis moleculaire 5A a ete retenu pour la superiorite de celui-ci sur d'autres adsorbants dans ce domaine de temperatures. Les problemes particuliers a l'adsorption en regime dynamique ont ete separement traites. Les isothermes d'adsorption d'azote ont ete tracees et la chaleur d'adsorp. tion calculee. (auteurs)

  11. Heterocyclic Anticancer Compounds: Recent Advances and the Paradigm Shift towards the Use of Nanomedicine's Tool Box.

    Martins, Pedro; Jesus, João; Santos, Sofia; Raposo, Luis R; Roma-Rodrigues, Catarina; Baptista, Pedro Viana; Fernandes, Alexandra R

    2015-09-16

    The majority of heterocycle compounds and typically common heterocycle fragments present in most pharmaceuticals currently marketed, alongside with their intrinsic versatility and unique physicochemical properties, have poised them as true cornerstones of medicinal chemistry. Apart from the already marketed drugs, there are many other being investigated for their promising activity against several malignancies. In particular, anticancer research has been capitalizing on the intrinsic versatility and dynamic core scaffold of these compounds. Nevertheless, as for any other promising anticancer drugs, heterocyclic compounds do not come without shortcomings. In this review, we provide for a concise overview of heterocyclic active compounds and families and their main applications in medicine. We shall focus on those suitable for cancer therapy while simultaneously addressing main biochemical modes of action, biological targets, structure-activity relationships as well as intrinsic limitation issues in the use of these compounds. Finally, considering the advent of nanotechnology for effective selective targeting of drugs, we shall discuss fundamental aspects and considerations on nanovectorization of such compounds that may improve pharmacokinetic/pharmacodynamic properties of heterocycles.

  12. Evolution of glycaemia in the blood of mice in the presence or absence of imidazole; Evolution de la glycemie sanguine chez la souris protegee ou non par l'imidazole

    Polverelli, M; Teoule, R [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    With respect to the radioprotective properties of the heterocyclic compound, imidazole, the authors followed the action of this product on blood sugar levels of mice X irradiated with a lethal dose. The main results of this work are: probably a hypo-glycemic action of the imidazole; an abolishment of the post-irradiation hyperglycemia by imidazole; an appreciably difference between male and female towards irradiation. (author) [French] Dans le cadre de l'etude des proprietes radioprotectrices de l'imidazole, nous nous sommes attaches a suivre l'action de ce produit sur le taux de glucose sanguin de souris irradiees a dose letale. Les principaux resultats de ce travail sont les suivants: l'action probablement hypoglycemiante de l'imidazole; en tant que radioprotecteur, cet heterocycle azote supprime l'hyperglycemie consecutive a l'irradiation; une difference assez sensible entre males et femelles vis-a-vis de l'irradiation. (auteur)

  13. Quenching of excited uranyl ion during its photochemical reduction with triphenyl-phosphine : Part IV - effect of heterocyclic molecules

    Sidhu, M.S.; Bhatia, P.V.K.

    1994-01-01

    The presence of heterocyclic compounds triggers off a competition between photophysical and photochemical annihilation of excited uranyl ion during its photochemical reduction with triphenylphosphine. This competition is used to measure Stern-Volmer constant using UV visible spectrophotometer for quenching the uranyl ion luminescence with a number of heterocyclic molecules viz., pyridine, thiophene bipyridyl, tetrahydrofuran and piperidine. (author). 7 refs., 2 figs., 1 tab

  14. Estilos estructurales del Subandino Sur de Bolivia

    Rocha, Emilio

    2013-01-01

    El Subandino Sur de Bolivia es una típica faja plegada y corrida de lámina delgada, con una notable regularidad en la geometría de las estructuras. Esta es una característica típica de las fajas plegadas en las que no se involucra el basamento en la deformación. Sin embargo, cuando se analiza en detalle la geometría y evolución de la deformación del Subandino Sur, se verifica que existen numerosas desviaciones de dicha regularidad. En el presente trabajo se estudiaron los diferentes procesos ...

  15. Synthesis and Regioselective Reaction of Some Unsymmetrical Heterocyclic Chalcone Derivatives and Spiro Heterocyclic Compounds as Antibacterial Agents.

    El-Hashash, Maher A; Rizk, Sameh A; Atta-Allah, Saad R

    2015-12-10

    A number of novel heterocyclic chalcone derivatives can be synthesized by thermal and microwave tools. Treatment of 4-(4-Acetylamino- and/or 4-bromo-phenyl)-4-oxobut-2-enoic acids with hydrogen peroxide in alkaline medium were afforded oxirane derivatives 2. Reaction of the epoxide 2 with 2-amino-5-aryl-1,3,4-thiadiazole derivatives yielded chalcone of imidazo[2,1-b]thiadiazole derivative 4 via two thermal routes. In one pot reaction of 4-bromoacetophenone, diethyloxalate, and 2-amino-5-aryl-1,3,4-thiadiazole derivatives in MW irradiation (W 250 and T 150 °C) under eco-friendly conditions afforded an unsuitable yield of the desired chalcone 4d. The chalcone derivatives 4 were used as a key starting material to synthesize some new spiroheterocyclic compounds via Michael and aza-Michael adducts. The chalcone 4f was similar to the aryl-oxo-vinylamide derivatives for the inhibition of tyrosine kinase and cancer cell growth. The electron-withdrawing substituents, such as halogens, and 2-amino-1,3,4-thiadiazole moeity decreasing the electron density, thereby decreasing the energy of HOMO, and the presence of imidazothiadiazole moiety should improve the antibacterial activity. Thus, the newly synthesized compounds were evaluated for their anti-bacterial activity against (ATCC 25923), (ATCC 10987), (ATCC 274,) and (SM514). The structure of the newly synthesized compounds was confirmed by elemental analysis and spectroscopic data.

  16. Structural and spectral comparisons between isomeric benzisothiazole and benzothiazole based aromatic heterocyclic dyes

    Wang, Yin-Ge; Wang, Yue-Hua; Tao, Tao; Qian, Hui-Fen; Huang, Wei

    2015-09-01

    A pair of isomeric heterocyclic compounds, namely 3-amino-5-nitro-[2,1]-benzisothiazole and 2-amino-6-nitrobenzothiazole, are used as the diazonium components to couple with two N-substituted 4-aminobenzene derivatives. As a result, two pairs of isomeric aromatic heterocyclic azo dyes have been produced and they are structurally and spectrally characterized and compared including single-crystal structures, electronic spectra, solvatochromism and reversible acid-base discoloration, thermal stability and theoretically calculations. It is concluded that both benzisothiazole and benzothiazole based dyes show planar molecular structures and offset π-π stacking interactions, solvatochromism and reversible acid-base discoloration. Furthermore, benzisothiazole based aromatic heterocyclic dyes exhibit higher thermal stability, larger solvatochromic effects and maximum absorption wavelengths than corresponding benzothiazole based ones, which can be explained successfully by the differences of their calculated isomerization energy, dipole moment and molecular band gaps.

  17. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    Behenna, Douglas C.

    2011-12-18

    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

  18. Synthesis and research of benzylamides of some isocyclic and heterocyclic acids as potential anticonvulsants.

    Strupińska, Marzanna; Rostafińska-Suchar, Grazyna; Pirianowicz-Chaber, Elzbieta; Stables, James P; Jiang, Jeff; Paruszewski, Ryszard

    2013-01-01

    A series of benzylamides of isocyclic and heterocyclic acids was synthesized and tested in Anticonvulsant Screening Project (ASP) of Antiepileptic Drug Development Program (ADDP) of NIH. Near all synthesized derivatives of heterocyclic acids showed activity. All obtained derivatives of mono- and bicyclic isocyclic acids were inactive. The power of action of heterocyclic acids derivatives seems does not depend upon kind of heteroatom (N, O or S). One of the compounds (2-furoic acid benzylamide (4)) appeared most promising. It showed in minimal clonic seizure (6Hz) test (ASP) in rats after i. p. administration: MES ED50 = 36.5 mg/kg, TOX TD50 = 269.75 mg/kg, and PI = 7.39.

  19. Heterocyclic N-Oxides – An Emerging Class of Therapeutic Agents

    Mfuh, Adelphe M.; Larionov, Oleg V.

    2016-01-01

    Heterocyclic N-oxides have emerged as potent compounds with anticancer, antibacterial, antihypertensive, antiparasitic, anti-HIV, anti-inflammatory, herbicidal, neuroprotective, and procognitive activities. The N-oxide motif has been successfully employed in a number of recent drug development projects. This review surveys the emergence of this scaffold in the mainstream medicinal chemistry with a focus on the discovery of the heterocyclic N-oxide drugs, N-oxide-specific mechanisms of action, drug-receptor interactions and synthetic avenues to these compounds. As the first review on this subject that covers the developments since 1950s to date, it is expected that it will inspire wider implementation of the heterocyclic N-oxide motif in the rational design of new medicinal agents. PMID:26087764

  20. Derisking the Cu-Mediated 18F-Fluorination of Heterocyclic Positron Emission Tomography Radioligands.

    Taylor, Nicholas J; Emer, Enrico; Preshlock, Sean; Schedler, Michael; Tredwell, Matthew; Verhoog, Stefan; Mercier, Joel; Genicot, Christophe; Gouverneur, Véronique

    2017-06-21

    Molecules labeled with fluorine-18 ( 18 F) are used in positron emission tomography to visualize, characterize and measure biological processes in the body. Despite recent advances in the incorporation of 18 F onto arenes, the development of general and efficient approaches to label radioligands necessary for drug discovery programs remains a significant task. This full account describes a derisking approach toward the radiosynthesis of heterocyclic positron emission tomography (PET) radioligands using the copper-mediated 18 F-fluorination of aryl boron reagents with 18 F-fluoride as a model reaction. This approach is based on a study examining how the presence of heterocycles commonly used in drug development affects the efficiency of 18 F-fluorination for a representative aryl boron reagent, and on the labeling of more than 50 (hetero)aryl boronic esters. This set of data allows for the application of this derisking strategy to the successful radiosynthesis of seven structurally complex pharmaceutically relevant heterocycle-containing molecules.

  1. Complexes of Th(IV) perchlorates, nitrates and thiocyanates with some heterocyclic bases

    Agarwal, R.K.; Srivastava, A.K.; Srivastava, M.; Bhakru, N.; Srivastava, T.N.

    1980-01-01

    Some Th(IV) perchlorate complexes of heterocyclic bases have been reported previously. Adducts of Th(IV) nitrates and thiocyanates with some heterocyclic N-oxides have been prepared and physico-chemical properties investigated. Comparatively little is known about the complexes of Th(IV) ion with the ligands containing nitrogen atom acting as electron donating centres. In view of this, the adducts of Th(IV) ion with certain nitrogen heterocyclic bases such as pyridine (Py), α-picoline (Pic), 2-amino pyridine (NH 2 Py), 2:4-lutidine (2,4LN), 2:6-lutidine, (2,6LN), quinoline (Q), isoquinoline (Isoq), 2,2'-bipyridine (Bipy) and 1,10-phenanthroline (Phen) were synthesised and characterised by analysis and IR absorption spectra. The results are presented and discussed. (author)

  2. Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications

    Thompson, Mark E.; Diev, Viacheslav; Hanson, Kenneth; Forrest, Stephen R.

    2015-08-18

    A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. The compounds can include structures of Formula I: ##STR00001## By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,.beta. fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.

  3. Comprehensive database of Manufactured Gas Plant tars. Part C. Heterocyclic and hydroxylated polycyclic aromatic hydrocarbons.

    Gallacher, Christopher; Thomas, Russell; Lord, Richard; Kalin, Robert M; Taylor, Chris

    2017-08-15

    Coal tars are a mixture of organic and inorganic compounds that were by-products from the manufactured gas and coke making industries. The tar compositions varied depending on many factors such as the temperature of production and the type of retort used. For this reason a comprehensive database of the compounds found in different tar types is of value to understand both how their compositions differ and what potential chemical hazards are present. This study focuses on the heterocyclic and hydroxylated compounds present in a database produced from 16 different tars from five different production processes. Samples of coal tar were extracted using accelerated solvent extraction (ASE) and derivatized post-extraction using N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) with 1% trimethylchlorosilane (TMCS). The derivatized samples were analysed using two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GCxGC/TOFMS). A total of 865 heterocyclic compounds and 359 hydroxylated polycyclic aromatic hydrocarbons (PAHs) were detected in 16 tar samples produced by five different processes. The contents of both heterocyclic and hydroxylated PAHs varied greatly with the production process used, with the heterocyclic compounds giving information about the feedstock used. Of the 359 hydroxylated PAHs detected the majority would not have been be detected without the use of derivatization. Coal tars produced using different production processes and feedstocks yielded tars with significantly different heterocyclic and hydroxylated contents. The concentrations of the individual heterocyclic compounds varied greatly even within the different production processes and provided information about the feedstock used to produce the tars. The hydroxylated PAH content of the samples provided important analytical information that would otherwise not have been obtained without the use of derivatization and GCxGC/TOFMS. Copyright © 2017 John Wiley & Sons, Ltd.

  4. Lactoperoxidase, an Antimicrobial Milk Protein, as a Potential Activator of Carcinogenic Heterocyclic Amines in Breast Cancer.

    Sheikh, Ishfaq Ahmad; Jiffri, Essam Hussain; Kamal, Mohammad Amjad; Ashraf, Ghulam Md; Beg, Mohd Amin

    2017-11-01

    Lactoperoxidase (LPO) is an antimicrobial protein secreted from mammary, salivary and other mucosal glands. It is an important member of heme peroxidase enzymes and the primary peroxidase enzyme present in breast tissues. In addition to the antimicrobial properties, LPO has been shown to be associated with breast cancer etiology. Heterocyclic amines, an important class of environmental and dietary carcinogens, have been increasingly associated with breast cancer etiology. Heterocyclic amines undergo activation in breast tissue as a result of oxidation by LPO. The current study includes three important heterocyclic amines, 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-1-methy-6-phenylimidazo[4,5-b]-pyridine (PhIP), that have carcinogenic activity. The structural binding characterization of IQ, MeIQx and PhIP with LPO was done using in silico approaches. Their binding pattern and interactions with LPO amino acid residues were analyzed. The three compounds bound in the distal heme cavity of LPO without replacing the important water molecule required for oxidation of substrate compounds. PhIP displayed lesser binding affinity for LPO in comparison to IQ and MeIQx. The binding mode of heterocyclic amines in distal heme cavity of LPO resembled to that of substrate binding pattern. The three heterocyclic amines are suggested to act as LPO substrate. The undisturbed water molecule present in distal heme cavity of the LPO is expected to facilitate the oxidation and activation of the three heterocyclic amines. These activated compounds may potentially bind with DNA in breast tissues forming DNA adducts and may subsequently lead to breast cancer initiation. Copyright© 2017, International Institute of Anticancer Research (Dr. George J. Delinasios), All rights reserved.

  5. Can creatine supplementation form carcinogenic heterocyclic amines in humans?

    Pereira, Renato Tavares dos Santos; Dörr, Felipe Augusto; Pinto, Ernani; Solis, Marina Yazigi; Artioli, Guilherme Giannini; Fernandes, Alan Lins; Murai, Igor Hisashi; Dantas, Wagner Silva; Seguro, Antônio Carlos; Santinho, Mirela Aparecida Rodrigues; Roschel, Hamilton; Carpentier, Alain; Poortmans, Jacques Remi; Gualano, Bruno

    2015-01-01

    Abstract Creatine supplementation has been associated with increased cancer risk. In fact, there is evidence indicating that creatine and/or creatinine are important precursors of carcinogenic heterocyclic amines (HCAs). The present study aimed to investigate the acute and chronic effects of low- and high-dose creatine supplementation on the production of HCAs in healthy humans (i.e. 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (8-MeIQx),  2-amino-(1,6-dimethylfuro[3,2-e]imidazo[4,5-b])pyridine (IFP) and 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx)). This was a non-counterbalanced single-blind crossover study divided into two phases, in which low- and high-dose creatine protocols were tested. After acute (1 day) and chronic supplementation (30 days), the HCAs PhIP, 8-MeIQx, IFP and 4,8-DiMeIQx were assessed through a newly developed HPLC–MS/MS method. Dietary HCA intake and blood and urinary creatinine were also evaluated. Out of 576 assessments performed (from 149 urine samples), only nine (3 from creatine and 6 from placebo) showed quantifiable levels of HCAs (8-MeIQx: n = 3; 4,8-DiMeIQx: n = 2; PhIP: n = 4). Individual analyses revealed that diet rather than creatine supplementation was the main responsible factor for HCA formation in these cases. This study provides compelling evidence that both low and high doses of creatine supplementation, given either acutely or chronically, did not cause increases in the carcinogenic HCAs PhIP, 8-MeIQx, IFP and 4,8-DiMeIQx in healthy subjects. These findings challenge the long-existing notion that creatine supplementation could potentially increase the risk of cancer by stimulating the formation of these mutagens. Key points There is a long-standing concern that creatine supplementation could be associated with cancer, possibly by facilitating the formation of carcinogenic heterocyclic amines (HCAs). This study provides compelling evidence

  6. Genetically modified CHO cells for studying the genotoxicity of heterocyclic amines from cooked foods

    Thompson, L.H.; Wu, R.W.; Felton, J.S.

    1995-07-01

    We have developed metabolically competent CHO cells to evaluate the genotoxicity associated with heterocyclic amines, such as those that are present in cooked foods. Into repair-deficient UV5 cells we introduced cDNAs for expressing cytochrome P450IA2 and acetyltransferases. We then genetically reverted these transformed lines to obtain matched metabolically competent repair-deficient/proficient lines. For a high mutagenic response, we find a requirement for acetyltransferase with IQ but not with PhIP. This system allows for both quantifying mutagenesis and analyzing the mutational spectra produced by heterocyclic amines

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

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

    2016-07-18

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

  8. New synthesis of photocurable silanes and polysiloxanes bearing heterocyclic or olefinic functions

    Youssef, B.; Lecamp, L.; Garin, S.; Bunel, C.

    1999-01-01

    In this work, we described the synthesis of silanes and polysiloxanes bearing cationic photopolymerizable groups. Two new methods were used. The first one is the reaction between 3-mercapto-propyl-1-triethoxysilane (1) and chloromethylated olefins by a phase transfer catalysis. The second one is the radical addition of (1) or poly(dimethylsiloxane-co-methylmercaptopropylsiloxane) (9) to allyl or vinyl substituted heterocyclic monomers. These methods led to the expected adducts with an excellent yield. The polysiloxanes bearing heterocyclic functional groups linked through thioether bonds were photocurable by cationic route. Under UV light intensity of 17.5 mW/cm 2 , these polymers harden after 15 or 20 s

  9. New chiral zwitterionic phosphorus heterocycles: synthesis, structure, properties and application as chiral solvating agents.

    Sheshenev, Andrey E; Boltukhina, Ekaterina V; Grishina, Anastasiya A; Cisařova, Ivana; Lyapkalo, Ilya M; Hii, King Kuok Mimi

    2013-06-17

    A family of new chiral zwitterionic phosphorus-containing heterocycles (zPHC) have been derived from methylene-bridged bis(imidazolines). These structures were unambiguously determined, including single-crystal XRD analysis for two compounds. The stability, acid/base and electronic properties of these dipolar phosphorus heterocycles were subsequently investigated. zPHCs can be successfully employed as a new class of chiral solvating agents for the enantiodifferentiation of chiral carboxylic and sulfonic acids by NMR spectroscopy. The stoichiometry and binding constants for the donor-acceptor complexes formed were established by NMR titration methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Screening for heterocyclic amines in chicken cooked in various ways.

    Solyakov, A; Skog, K

    2002-08-01

    Chicken cooked under well-controlled conditions and commercial chicken products were screened for heterocyclic amines (HAs). Chicken samples were boiled, deep-fried, pan-fried, oven-roasted, cooked in an unglazed clay pot or in a roasting bag in the oven, and oven broiled. 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 1-methyl-9H-pyrido[3,4-b]indole (harman) and 9H-pyrido[3,4-b]indole (norharman) were identified in several samples. Chicken cooked at low temperatures contained low amounts of HAs. In pan-fried chicken breasts, MeIQx was detected in amounts below 2 ng/g, 4,8-DiMeIQx below 0.6 ng/g, and PhIP in amounts up to 38 ng/g. Harman and norharman were detected in almost all samples (below 15 ng/g). In skin from a commercially barbecued chicken, MeIQx, 4,8-DiMeIQx and PhIP were detected, while only traces of MeIQx were detected in the meat. MeIQx was detected in a commercial chicken flavour, 0.1 ng/ml. No HAs were detected in pan-fried chicken liver. The results show that the content of HAs in chicken cooked in various ways is low if prepared at low temperatures, and increases with increasing cooking temperature. PhIP formation seems to start accelerating at cooking temperatures around or above 200 degrees C. Colour development increases with cooking temperature, but no correlation with HA content was observed.

  11. Predictors of dietary heterocyclic amine intake in three prospective cohorts.

    Byrne, C; Sinha, R; Platz, E A; Giovannucci, E; Colditz, G A; Hunter, D J; Speizer, F E; Willett, W C

    1998-06-01

    Cooking meat creates heterocyclic amines (HCAs) through pyrolysis of amino acids and creatinine. Although recognized as mutagenic, the etiological role of HCA in human cancer is unclear, due to the lack of information on the effect of typical food cooking methods on HCA concentrations and on variation in HCA exposure in populations. We estimated overall daily dietary HCA intake and variation in intake between individuals, using recent data on HCA concentrations in various meats prepared by cooking methods, temperatures, and times common in United States in the 1990s. Random samples of 250 participants from each of three large prospective cohorts were mailed a questionnaire to assess frequency of consumption, cooking method, and typical outside appearance of pan-fried, broiled, and grilled or barbecued chicken, fish, hamburger, and steak; fried, microwaved, and broiled bacon; fried sausage; roast beef; and homemade gravy. The 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), and 2-amino-3,4,8-trimethylimidazo[4,5,f]quinoxaline (DiMeIQx) concentrations, measured in composite samples by solid-phase extraction and high-performance liquid chromatography, were assigned to each food, cooking method, and doneness level. The dietary reports showed approximately 30-fold relative variation in 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline intake, 20-fold for 2-amino- -methyl-6-phenylimidazo[4,5-b]pyridine, and over 110-fold for 2-amino-3,4,8-trimethylimidazo[4,5,f]quinoxaline, when the 10th and 90th percentiles of HCA intake were compared (90th/10th percentile value). These reported variations in HCA exposure among participants in these three large cohorts indicates that estimation of HCA intake and determination of association with disease risk are feasible, if additional information on meat cooking methods is obtained.

  12. Analyse de l'effet de la suréducation sur l'efficacité technique des ...

    de tire-au-flanc, et l'état de santé (Vroom 1964 ; Sheppard & Herrick 1972 ; ... impact négatif significatif de la suréducation sur la satisfaction au travail ; son ..... présence syndicale sur la performance financière de 250 entreprises américaines.

  13. Étude sur l'entrepreneuriat dalit : Regard sur 25 % de la population ...

    Étude sur l'entrepreneuriat dalit : Regard sur 25 % de la population indienne. Cette étude, pilotée par Udit Raj, député du parlement indien, aide à mieux comprendre les contraintes que rencontrent les entrepreneurs dalits. Elle permettra de sonder 12 000 entrepreneurs dalits dans 14 états et de recueillir des données ...

  14. Étude du Partenariat de recherche sur l'influenza aviaire en Asie sur ...

    Étude du Partenariat de recherche sur l'influenza aviaire en Asie sur l'efficacité des mesures de lutte. L'influenza aviaire hautement pathogène (H5N1) est une grave maladie qui touche la volaille et contamine les êtres humains dans une faible proportion. L'Organisation mondiale de la santé croit que le virus pourrait subir ...

  15. Synthesis, electrochemical, structural and theoretical study of new derivatives of OABAN and OABAO heterocycles

    Mikysek, T.; Kvapilová, Hana; Doušová, H.; Josefík, F.; Šimůnek, P.; Růžičková, Z.; Ludvík, Jiří

    2017-01-01

    Roč. 455, č. 2 (2017), s. 465-472 ISSN 0020-1693 R&D Projects: GA MŠk LD14129 Institutional support: RVO:61388955 Keywords : boron heterocycles * synthesis * electrochemistry Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 2.002, year: 2016

  16. N,N'-diamidoketenimines via coupling of isocyanides to an N-heterocyclic carbene.

    Hudnall, Todd W; Moorhead, Eric J; Gusev, Dmitry G; Bielawski, Christopher W

    2010-04-16

    Treatment of an N-heterocyclic carbene that features two amide groups N-bound to the carbene nucleus with various organic isocyanides afforded a new class of ketenimines in yields of up to 96% (isolated). DFT analyses revealed that the carbene exhibits a unique, low-lying LUMO, which may explain the atypical reactivity observed.

  17. N-heterocyclic carbene copper(I) catalysed N-methylation of amines using CO2

    Santoro, Orlando

    2015-09-30

    The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(I) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.

  18. Identification of the Eight-Membered Heterocycles Hicksoanes A-C from the Gorgonian Subergorgia hicksoni

    Řezanka, Tomáš; Hanuš, L. O.; Dembitsky, V. M.; Sigler, Karel

    2008-01-01

    Roč. 2008, č. 7 (2008), s. 1265-1270 ISSN 1434-193X R&D Projects: GA MŠk 1P05OC073 Institutional research plan: CEZ:AV0Z50200510 Keywords : gorgonians * nitrogen heterocycles * natural products Subject RIV: EE - Microbiology, Virology Impact factor: 3.016, year: 2008

  19. MICROWAVE IRRADIATION IN BENIGN SYNTHESIS OF HETEROCYCLES, NOBLE NANOMETALS AND NANOCOMPOSITES

    A brief historic account of reactions involving microwave (MW) exposure of neat reactants or catalyzed by mineral support surfaces, such as alumina, silica, clay, or their ‘doped’ versions, for the rapid one-pot assembly of heterocyclic compounds [1] from in situ generated reacti...

  20. Study of physicochemical properties of zinc(II) butyrate complex compounds with some heterocyclic ligands

    Szakácsová, M.; Györová, K.; Szunyogová, E.; Kovářová, Jana

    2002-01-01

    Roč. 96, - (2002), s. 383 ISSN 0009-2770. [Meeting of Chemical Societies /54./. 30.06.2002-04.07.2002, Brno] R&D Projects: GA AV ČR KSK4050111; GA MŠk VEGA 1/9247/02; GA MŠk VEGA 047/074 Keywords : butyrate complex compounds * heterocyclic ligands Subject RIV: CD - Macromolecular Chemistry

  1. Mixed-ligand complexes of zirconium (IV) and uranium with salicylaldehyde and some heterocyclic azopyrazolones

    Amrallahi, A.H.

    1994-01-01

    Mixed-ligand complexes of Zr(IV) and U(IV) with salicylaldehyde (SA) and some heterocyclic azopyrazolenes have been studied spectrophotometrically. All formed chelates have ratio 1:1:1. The stoichiometry and stability of the binary mixed chelates been evaluated. Elemental analysis, molar conductance and IR spectra have been used for identification of solid mixed complexes. (author)

  2. Greener Synthesis of N-Heterocycles via Sustainable Applications of Nano-Catalysts

    A brief historic account of reactions involving microwave (MW) exposure of neat reactants or catalysis by mineral surfaces, such as alumina, silica, clay, or their ‘doped’ versions, for the rapid one-pot assembly of heterocyclic compounds from in situ generated reactive intermedi...

  3. Bent Shaped 1,3,4-Oxadiazole/Thiadiazole heterocyclic rings ...

    Two series of bent shaped 1,3,4-oxadiazole/thiadiazole heterocyclic ring containing liquid crystalline (LC) compounds were synthesized and characterized by FT-IR, 1H, 13C-NMR and ESI-Mass spectro-scopic techniques. Liquid crystal properties were investigated by polarized optical microscopy and differential scanning ...

  4. Design, synthesis and antibreast cancer MCF-7 cells biological evaluation of heterocyclic analogs of resveratrol.

    Du, Cheng; Dong, Ming-Hui; Ren, Yu-Jie; Jin, Lu; Xu, Cheng

    2017-09-01

    A new series of resveratrol heterocyclic analogs (4a-m) were designed and synthesized, and their inhibitiory effects on MCF-7 cells were evaluated to investigate structure-activity relationship. The effects of these analogs on human breast cancer MCF-7 cells were also determined. Results showed that MCF-7 cells could be inhibited more potently by these analogs than by resveratrol (IC 50  = 80.0 μM). Among the analogs, compounds 4c, 4e, and 4k showed a significantly higher activity (IC 50  = 42.7, 48.1, and 43.4 μM) than resveratrol. Furthermore, the derivatives without additional heterocyclic structure in the 4'-OH position exhibited a more potent activity than that with addition heterocyclic structure. In addition, docking simulation was performed to adequately position compound 4c in a human F 1 -ATPase active site to determine a probable binding model. These heterocyclic analogs could be effective candidates for the chemoprevention of human breast cancer.

  5. Synthesis of acetylene alcohols of heterocyclic type and the acyl derivatives

    Moldir Dyusebaeva

    2015-03-01

    Full Text Available A synthesis of potentially biologically active heterocyclic amino alcohols of acetylene (Piperidine and Morpholine under the conditions of Mannich reaction accomplished and received their acyl derivatives. Pharmacological activity (antibacterial and antispasmotic of synthesized compounds, also acute toxicological characteristics studied. The study showed that the combination of DMAE-4 has antispasmodic activity with low toxicity.

  6. Enaminone in heterocyclic synthesis: synthesis of new pyrazolopyrazole, pyrazolothienooxazine and pyrazolothienopyridine derivatives

    Hafiz, I.S.; Rahim, M.A.M.A.

    2014-01-01

    The chemical reactivity of enaminone 2 toward some nucleophilic and electrophilic reagents was investigated. Enaminone 2 was used as a key precursor for the synthesis of many important heterocyclic compounds. The synthesized compounds were characterized by IR, 1H-NMR, MS spectral and elemental analysis. (author)

  7. Complexes of uranyl with N-oxides of heterocyclic amines. Electron-vibrational absorption spectra

    Jezowska-Trzebiatowska, B.; Wieczorek, M.

    1977-01-01

    A number of coordination compounds formed by uranyl chloride and nitrate with N-oxides of heterocyclic amines have been prepared and characterized by spectral measurements in the absorption region 20000-50000 cm -1 . The electrons and vibronic transitions have been determined and discussed. (author)

  8. Correlations between electrochemical and spectrochemical parameters of ruthenium sulfoxides series with N-heterocyclic

    Oliveira, D. de; Toma, H.E.

    1990-01-01

    A systematic study of Ru Cl sub(2) (DMSO) sub(2) L sub(2) derivates, where L = N-heterocyclic base is described, contributing for a best understanding of chemical behaviour and electronic structure of the ruthenium sulfoxides. The correlations between the electrochemical and the spectroscopical parameters of the serie are presented with more emphasis. (author)

  9. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    Zhao, Changgui; Guo, Donghui; Munkerup, Kristin; Huang, Kuo-Wei; Li, Fangyi; Wang, Jian

    2018-01-01

    on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a

  10. N-Heterocyclic carbene functionalized goup 7-9 transition metal

    Aktas, H.; Slootweg, J.C.; Ehlers, A.W.; Lutz, M.; Spek, A.L.; Lammertsma, K.

    2009-01-01

    The N-heterocyclic carbene (NHC) functionalized phosphinidene complexes [(pCy)(IiPr2Me2)- RudPMes*] (4), [(pCy)(IiPr2Me2)OsdPMes*] (6), and [(Cp*)(IiPr2Me2)RhdPMes*] (7) were generated by a double-dehydrohalogenation-ligation sequence of the corresponding primary phosphine complexes with 3 equiv of

  11. Mechanistic Investigation of the Ruthenium–N-Heterocyclic-Carbene-Catalyzed Amidation of Alcohols and Amines

    Makarov, Ilya; Fristrup, Peter; Madsen, Robert

    2012-01-01

    The mechanism of the ruthenium–N-heterocyclic-carbene-catalyzed formation of amides from alcohols and amines was investigated by experimental techniques (Hammett studies, kinetic isotope effects) and by a computational study by using dispersion-corrected density functional theory (DFT/ M06...

  12. Expedient Access to an N -phenylpyrrolidin-2-yl Heterocycle via a ...

    Expedient Access to an N -phenylpyrrolidin-2-yl Heterocycle via a Base-Induced Intramolecular aza -Michael Reaction. ... in good overall yield when employing a stoichiometric amount of base to facilitate the intramolecular aza-Michael reaction. Keywords: aza Michael, intramolecular, catalysed, piperidine, pyrrolidine, base ...

  13. New Chiral Zwitterionic Phosphorus Heterocycles: Synthesis, Structure, Properties and Application as Chiral Solvating Agents

    Sheshenev, A. E.; Boltukhina, E. V.; Grishina, Anastasia; Císařová, I.; Lyapkalo, Ilya; Hii, K. K.

    2013-01-01

    Roč. 19, č. 25 (2013), s. 8136-8143 ISSN 0947-6539 Grant - others:7th European Community Framework Programme(XE) FP7-252247 Institutional support: RVO:61388963 Keywords : binding constants * chirality * enantioselectivity * NMR spectroscopy * phosphorus heterocycles * zwitterions Subject RIV: CC - Organic Chemistry Impact factor: 5.696, year: 2013

  14. N-heterocyclic carbene copper(I) catalysed N-methylation of amines using CO2

    Santoro, Orlando; Lazreg, Faï ma; Minenkov, Yury; Cavallo, Luigi; Cazin, Catherine S. J.

    2015-01-01

    The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(I) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.

  15. Bis-ligated Ti and Zr complexes of chelating N-heterocyclic carbenes

    El-Batta, Amer; Waltman, Andrew W.; Grubbs, Robert H.

    2011-01-01

    In this communication we report the synthesis of novel titanium and zirconium complexes ligated by bidentate "salicylaldimine-like" N-heterocyclic carbenes (NHC). Double addition of the NHC chelate to either TiCl4(thf)2 or ZrCl4 forms bis

  16. Dietary exposure to heterocyclic amines in a Chinese population.

    Wong, Kin-Yoke; Su, Jin; Knize, Mark G; Koh, Woon-Puay; Seow, Adeline

    2005-01-01

    Heterocyclic aromatic amines (HAAs) formed in meat during high-temperature cooking have been associated with risk of colorectal and breast cancer. Incidence of these cancers is increasing in Singapore, a country with 77% ethnic Chinese. The purpose of this study was to estimate HAA levels in the Chinese diet and individual levels of exposure to these compounds because little is known. Twenty-five samples (each pooled from three sources) of meat and fish, cooked as commonly consumed, were analyzed by high-performance liquid chromatography for concentrations (ng/g) of 2-amino-3-methylimidazo[4,5-f]quinoline, 2-amino-3, 4-dimethylimidazo[4,5-f]quinoline (MeIQ), 2-amino-3,8- dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3, 4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx), 2- amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline, 2-amino -1,6-dimethylfuro[3,2-e]imidazo[4,5-b]pyridine, and 2- amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP). Dietary meat consumption data (g/day), including meat type and cooking method, were gathered from food-frequency questionnaires completed by 497 randomly sampled Chinese men and women aged 20-59 yr. PhIP, MeIQx, and 4,8-DiMeIQx were the most abundant HAAs detected. Total HAA concentrations ranged from roasted pork had the highest levels. The estimated mean daily exposure to HAA was 49.95 ng/day (P10 14.0 ng/day, P90 95.8 ng/day); this was 50% higher among younger (20-39 yr) compared with older individuals. Seven specific meat-cooking method combinations contributed 90.1% of this intake, namely, pan-fried fish, pork, and chicken, deep-fried chicken as well as fish, roasted/barbecued pork, and grilled minced beef.

  17. Photolysis of Heterocyclic Lactones in Cryogenic Inert Matrices

    Kus, N.

    2008-01-01

    Heterocyclic lactones receive important uses in organic synthesis and are important biologically active compounds. Their weak toxicity and easy synthesis have made these compounds the subject of great interest and extensive investigation. Since long ago, lactones have been shown to possess an interesting photochemistry. Some representative six- and five-membered conjugated lactones [α-pyrone and some of its derivatives, including coumarin and 3-acetamido coumarin, 2(5H)-furanone] were recently investigated by infrared spectroscopy using the matrix isolation technique and quantum chemical calculations in our laboratories. Two main competitive photochemical reaction pathways could be identified: (i) ring-opening, leading to formation of the isomeric aldehyde-ketene, and (ii) ring-contraction leading to the corresponding Dewar isomers. For α-pyrone and 2(5H)-furanone, the ring-opening process dominates over the ring-contraction reaction, the same occurring for derivatives of these compounds bearing a voluminous substituent at position 3. In 2(5H)-furanone, the ring-opening reaction requires the simultaneous occurrence of a [1,2]-hydrogen atom migration, which was found to occur upon excitation at λ> 235 nm. Under the identical UV-irradiation (λ> 235 nm) of the six-membered analogues, the ring-opening reaction was more efficient in α-pyrone than in coumarin, and factors explaining this observation will be discussed. In turn, the Dewar forms of the studied compounds, resulting from the ring-contraction photoreaction, were found to undergo subsequent photo-elimination of CO 2 , with formation of the corresponding cycloalkenes. In the matrices, CO 2 and the simultaneously formed cycloalkenes were predicted by calculations to exist as associates, in which the CO 2 molecule is preferentially placed over the cycloalkene ring in a stacked-type geometry. For coumarin, a third photoreaction channel was observed, leading to formation of benzofurane and CO. This additional

  18. U.S. dietary exposures to heterocyclic amines.

    Bogen, K T; Keating, G A

    2001-01-01

    Heterocyclic amines (HAs) formed in fried, broiled or grilled meats are potent mutagens that increase rates of colon, mammary, prostate and other cancers in bioassay rodents. Studies of how human dietary HA exposures may affect cancer risks have so far relied on fairly crudely defined HA-exposure categories. Recently, an integrated, quantitative approach to HA-exposure assessment (HAEA) was developed to estimate compound-specific intakes for particular individuals based on corresponding HA-concentration estimates that reflect their meat-type, intake-rate, cooking-method and meat-doneness preferences. This method was applied in the present study to U.S. national Continuing Survey of Food Intakes by Individuals (CSFII) data on meats consumed and cooking methods used by >25,000 people, after adjusting for underreported energy intake and conditional on meat-doneness preferences estimated from additional survey data. The U.S. population average lifetime time-weighted average of total HAs consumed was estimated to be approximately 9 ng/kg/day, with 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) estimated to comprise about two thirds of this intake. Pan-fried meats were the largest source of HA in the diet and chicken the largest source of HAs among different meat types. Estimated total HA intakes by male vs. female children were generally similar, with those by (0- to 15-year-old) children approximately 25% greater than those by (16+-year-old) adults. Race-, age- and sex-specific mean HA intakes were estimated to be greatest for African American males, who were estimated to consume approximately 2- and approximately 3-fold more PhIP than white males at ages <16 and 30+ years, respectively, after considering a relatively greater preference for more well-done items among African Americans based on national survey data. This difference in PhIP intakes may at least partly explain why prostate cancer (PC) kills approximately 2-fold more African American than white men

  19. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    Huang, Qinhua [Iowa State Univ., Ames, IA (United States)

    2004-12-19

    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I2, ICl, PhSeCl, PhSCl and p-O2NC6H4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement

  20. Advances in heterocycle synthesis via [3+m]-cycloaddition reactions involving an azaoxyallyl cation as the key intermediate.

    Xuan, Jun; Cao, Xia; Cheng, Xiao

    2018-05-17

    Heterocyclic compounds are widely found in many natural isolates and medicinally relevant compounds, as well as some fine chemicals. The development of general and efficient methods for the construction of heterocyclic compounds is one of the most important tasks in synthetic organic chemistry. Along these lines, [3+m]-cycloaddition reactions involving in situ generated azaoxyallyl cations as the 3-atom units have emerged as a powerful method for the synthesis of nitrogen-containing heterocycles. In this feature article, we highlight recent advances in this rapidly growing area, mainly focusing on the reaction design as well as the reaction mechanism.

  1. Structure of radicals produced by γ radiolysis. Part 4. Adamantane matrices doped with various 5-membered heterocyclic molecules

    Winters, D.L.; Ling, A.C.

    1976-01-01

    The effects of γ-radiolysis at room temperature on adamantane and adamantane-d 16 matrices doped with 5-membered heterocyclic molecules has been examined by X-band electron spin resonance (esr) spectrometry. Radical structures formed from heterocyclic solute molecules are discussed and tentative assignments made. Discussion of possible radical structures derived from selected heterocyclic compounds is included, but unambiguous assignmens of structure cannot be made for these compounds from the esr data obtained. It was noted that perdeuterated adamantane matrices provided superior resolution for esr spectra derived from radicals with a delocalized spin center such as allyl or allenyl species. (author)

  2. Action des pots catalytiques sur les polluants non réglementés How Catalytic Mufflers Act on Unregulated Pollutants

    Degobert P.

    2006-11-01

    Full Text Available L'installation de pots catalytiques sur les véhicules, envisagée essentiellement pour réduire le niveau des polluants actuellement réglementés (oxyde de carbone, hydrocarbures imbrûlés, oxydes d'azote, aura-t-elle des effets bénéfiques ou néfastes sur les polluants non réglementés ? Pour éclaircir cette question, cette étude compare sur des véhicules les plus comparables possibles du point de vue conception et équipements, les émissions des voitures non dépolluées et celles de voitures dépolluées , c'est-à-dire équipées de pots catalytiques d'oxydation, de pots catalytiques multifonctionnels ou de systèmes de combustion en mélange pauvre. Les polluants non réglementés pris en considération sont les aldéhydes, les sulfates, l'anhydride sulfureux, l'hydrogène sulfuré, l'oxysulfure de carbone, le cyanogène, l'acide cyanhydrique, l'acide nitrique, les aromatiques légers, les hydrocarbures aromatiques polycycliques, ces derniers en liaison avec leurs propriétés mutagènes. Le catalyseur a été considéré dans différents états : neuf, vieilli, empoisonné : l'influence des déréglages des systèmes de contrôle (avance, sonde à oxygène, allumage, etc. a été prise en compte. Il apparaît que la présence de catalyseur fonctionnant dans des conditions normales se révèle en général bénéfique sur la majorité des polluants ou tout au moins indifférente sur certains polluants. En outre les déréglages éventuels n'entraîneraient pas de concentrations alarmantes de ces polluants non réglementés. Will the equipping of vehicles with catalytic mufflers, planned mainly to reduce the level of currently regulated pollutants (carbon monoxide, unburned hydrocarbons , nitrogen oxides, have a beneficial or harmful effect on unregulated pollutants? To elucidate this question this article considers the vehicles that are the most comparable possible from the standpoint of design and equipment to compare emissions

  3. Enquêtes sur les soucoupes volantes

    Lagrange, Pierre

    2007-01-01

    La dispute autour du mot « preuve » se réduit à une question : Qu'est-ce qui constitue une preuve ? Faut-il qu'un ovni atterrisse à l'entrée du Pentagone, près des bureaux des chefs d'État-Major ? Ou bien est-ce une preuve quand une station de radar au sol détecte un ovni, envoie un jet l'intercepter, que le pilote du jet le voit et le suit sur son radar pour finir par le voir disparaître à une vitesse phénoménale ? Ou est-ce une preuve quand un pilote tire sur un ovni et maintient son histoi...

  4. Oligocene cetaceans from Baja California Sur, Mexico

    Hernández Cisneros, Atzcalli Ehécatl; González Barba, Gerardo; Fordyce, Robert Ewan

    2017-01-01

    Abstract Baja California Sur has an important Cenozoic marine fossil record which includes diverse but poorly known Oligocene cetaceans from Mexico. Here we review the cetacean fossil record including new observations from materials that elucidate the evolution of the Neoceti in the Pacific basin. Fossils were collected from outcrops of the El Cien Formation (Oligocene-Early Miocene) and from San Gregorio Formation (Late Oligocene). The specimens belong to the paleontological collection of Mu...

  5. Controverses sur les sucres [Controversies about sugars

    Malika BOUCHENAK

    2016-12-01

    Full Text Available La surconsommation de sucres ajoutés et leurs effets putatifs sur diverses pathologies cardiométaboliques continuent de susciter des controverses. Dans les années 1950, le taux élevé de maladies cardiovasculaires (MCV, chez les hommes Américains a conduit à des études sur le rôle des facteurs alimentaires, tels que le cholestérol, les phytostérols, l'excès de calories, les acides aminés, les graisses, les glucides, les vitamines et les minéraux, à influencer le risque de MCV. Dans les années 60, deux éminents physiologistes, plaidant pour des hypothèses causales divergentes de MCV, John Yudkin a identifié les sucres ajoutés comme agent primaire, tandis que Ancel Keys identifiait les graisses totales, les graisses saturées et le cholestérol alimentaire. Cependant, dans les années 80, peu de scientifiques croyaient que les sucres ajoutés jouaient un rôle important dans la maladie coronarienne, et les premiers conseils nutritionnels de 1980 (1980 Dietary Guidelines for americans étaient axés sur la réduction des graisses totales, des graisses saturées et du cholestérol alimentaire pour la prévention des MCV.

  6. Unión del magreb, un caso de regionalismo Sur-Sur

    SofianE Bouhdiba

    2009-01-01

    Full Text Available Se exploran brevemente las fuerzas y limitaciones de la Unión del Magreb (UMA como una experiencia de regionalismo Sur-Sur, en el marco de mayor extensión. Se plantea la necesidad de que la UMA redireccione sus intereses, estrategias y alianzas hacia el sur, puesto que se ha vuelto un instrumento de intercambios comerciales con la Unión Europea y un eje estratégico de lucha contra el terrorismo para Estados Unidos. Además se invita a la misma UMA a que considere los alcances de instituciones de integración en América Latina y Asia a fin de fortalecerse como bloque.

  7. Role of certain plant natural products or gamma radiation in the control of mutagenic activity of some heterocyclic amines

    Abu Ghadeer, A.R.M.; El-Sedeek, A.B.A.; Salem, A.M.; Abu Zaid, M.M.

    1999-01-01

    The present study was designed to use ames test to evaluate the antimutagenic effect of some natural products on the lever microsomes extracted from rats and incubated with some chemical mutagens (heterocyclic compounds). Male swiss albino rats (120-140 g) were used as the source of liver microsomes. Three natural products (Nigella extract, garlic powder and sesame oil) were used to evaluate their antimutagenic activities on six heterocyclic amines. All the tested natural products exhibited their antimutagenic activities when added to the investigated heterocyclic compounds and the most effective product was nigella sativa. another group of rats was exposed to gamma-radiation (6.5 Gy) for testing the validity of ames test in quantitating mutagenicity using liver microsomes of irradiated rats. Liver microsomes from irradiated rats showed to lose ability for metabolic activation needed for heterocyclic amines to exert their mutagenic effect on salmonella typhimurium

  8. The investigation of hydrogens bonds between sulphur-bearing heterocyclic and proton-donor compounds by IR absorption spectra

    Narziev, B.N.; Nurulloev, M.; Makhkambaev, D.

    1982-01-01

    In this article the results of intermolecular interaction study of sulfur-containing heterocyclic (thiophene, thiophane) and proton-donar (water, alcohol, carbonic acids, chlorophon) molecules for measuring of IR spectrum absorption of protondonar compounds in soluted shape are presented

  9. El (los Sur buscando al Sur. Una construcción entre estereotipos y realidad.

    Mabel Franzone

    2010-11-01

    Full Text Available Todas las lecturas que podamos hacer del Sur, de sus propias representaciones, de aquellas vehiculizadas por el Norte, de sus creaciones, de sus reacciones, de su búsqueda constante de identidad, son lecturas de múltiples situaciones, que llaman a cruces insoslayables entre pueblos, entre distintas etnias, entre disciplinas, entre sentimientos que van desde el rechazo hasta la atracción casi magnética entre los dos hemisferios. Nuestra intención primera era la de reunir de manera aproximativa las problemáticas actuales de los Sur, ligadas a lo imaginario.

  10. Fluoroalkyl Amino Reagents (FARs: A General Approach towards the Synthesis of Heterocyclic Compounds Bearing Emergent Fluorinated Substituents

    Bruno Commare

    2017-06-01

    Full Text Available Fluorinated heterocycles are important building blocks in pharmaceutical, agrochemical and material sciences. Therefore, organofluorine chemistry has witnessed high interest in the development of efficient methods for the introduction of emergent fluorinated substituents (EFS onto heterocycles. In this context, fluoroalkyl amino reagents (FARs—a class of chemicals that was slightly forgotten over the last decades—has emerged again recently and proved to be a powerful tool for the introduction of various fluorinated groups onto (heteroaromatic derivatives.

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

    Chen, Ming Z.; Micalizio, Glenn C.

    2009-01-01

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

  12. Fluoroalkyl Amino Reagents (FARs): A General Approach towards the Synthesis of Heterocyclic Compounds Bearing Emergent Fluorinated Substituents.

    Commare, Bruno; Schmitt, Etienne; Aribi, Fallia; Panossian, Armen; Vors, Jean-Pierre; Pazenok, Sergiy; Leroux, Frédéric R

    2017-06-12

    Fluorinated heterocycles are important building blocks in pharmaceutical, agrochemical and material sciences. Therefore, organofluorine chemistry has witnessed high interest in the development of efficient methods for the introduction of emergent fluorinated substituents (EFS) onto heterocycles. In this context, fluoroalkyl amino reagents (FARs)-a class of chemicals that was slightly forgotten over the last decades-has emerged again recently and proved to be a powerful tool for the introduction of various fluorinated groups onto (hetero)aromatic derivatives.

  13. Stereoselective, nitro-Mannich/lactamisation cascades for the direct synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles

    Pavol Jakubec

    2012-04-01

    Full Text Available A versatile nitro-Mannich/lactamisation cascade for the direct stereoselective synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles has been developed. A highly enantioenriched substituted 5-nitropiperidin-2-one was synthesised in a four component one-pot reaction combining an enantioselective organocatalytic Michael addition with the diastereoselective nitro-Mannich/lactamisation cascade. Protodenitration and chemoselective reductive manipulation of the heterocycles was used to install contiguous and fully substituted stereocentres in the synthesis of substituted piperidines.

  14. Effet de la co-inoculation du rhizobium et de mycorhizes sur les ...

    SARAH

    30 déc. 2013 ... RÉSUMÉ. Objectif : Les sols sahéliens se caractérisent par une faible fertilité dont l'amélioration se fait par la pratique de la jachère ou l'apport du fumier. La fixation de l'azote atmosphérique par certaines légumineuses est peu performante voir inefficace. De nos jours, l'inoculation de rhizobium et de ...

  15. Sur la plurifonctionnalité du discours direct

    Cigada Sara

    2012-01-01

    La comparaison entre les résultats de nombreux travaux sur le dialogue dans le texte littéraire, sur l’attestation linguistique de la subjectivité, sur la fonction argumentative des émotions dans le discours et sur les effets de polyphonie, suggère que la structure sémiotique et linguistique du discours direct (DD) se trouve au croisement stratégique de plusieurs axes de la construction discursive. Nous étudions donc l’insertion du DD dans le discours (cf. Rosier 2008: Le discours rapporté en...

  16. Creation, synthesis and characterisation of nitrogenous poly-heterocyclic new molecules for specific complexation of metallic cations; Conception, synthese et caracterisation de molecules polyheterocycliques azotees pour la complexation specifique de cations metalliques

    Dupont, C.

    2010-12-10

    radioelements a vie longue, pour reduire les quantites et la nocivite des dechets radioactifs ultimes. Ces dechets issus du retraitement du combustible nucleaire use sont actuellement vitrifies a La Hague. Ainsi, le projet 'separation poussee' vise a completer le procede industriel PUREX par le developpement de procedes permettant d'extraire les actinides mineurs des raffinats PUREX ou se trouvent egalement des produits de fission constitues principalement de lanthanides, neutrophages. Pour realiser la separation poussee, les actinides mineurs des raffinats PUREX doivent etre separes par des molecules specifiques. Les BTP ou bis-triazinyl-pyridines ont ete largement etudiees au CEA pour la separation actinides(III)/lanthanides(III). Elles complexent selectivement les actinides, mais l'origine de cette selectivite n'est pas completement expliquee: notamment l'influence des groupements (attaches a leur structure) sur la complexation ou la selectivite reste a demontrer. En outre, elles sont sensibles a l'hydrolyse et a la radiolyse. La premiere partie du travail presente la synthese de BTP ou de BTBP, differemment substituees pour ameliorer leur resistance face a l'hydrolyse ou a la radiolyse, et une nouvelle famille de ligands polyaromatiques azotes: les BPBT, presentant un enchainement original de cycles pyridine et triazine, different de toutes les structures decrites jusqu'a present dans la litterature. La seconde partie de ce travail est consacree a l'etude physico-chimique de nouvelles molecules obtenues, en determinant leurs constantes de protonation et de complexation, pour connaitre l'influence des differents groupements sur la complexation et la selectivite. Enfin, le troisieme volet concerne l'etude des proprietes de ces ligands en extraction liquide-liquide, utilises soit comme extractants lipophiles, soit comme complexants hydrophiles. (auteur)

  17. Physical and chemical study of the influence of oxidation on the structure of carbon black; Etude physico-chimique de l'influence de l'oxydation sur la structure du noir de carbone

    Hueber, Francois

    1961-06-26

    This research thesis reports the study of the influence of an oxidising attack on carbon black particles by using chemical, physical and electrochemical methods to highlight the oxidation process. The carbon black particle is a spherical set essentially made of amorphous and crystalline carbon. It appears that the oxidising attack mainly occurs against the amorphous parts which surround the crystallites. If the attack is strong enough, crystallites are freed and the particle collapses. This process has been observed by using electronic microscopy, X rays, the BET nitrogen absorption method, and infra-reds. Chemical analysis revealed the presence of carboxyl, hydroxyl and quinone functional groups on the oxidised particle surface. These groups have been dosed by different methods (methylation, calcium acetate dosing, polarography and potassium borohydride reduction) [French] Dans la presente etude nous nous sommes occupes de l'influence de l'attaque oxydante sur les particules de noir de carbone. Pour ce faire, nous avons mis en oeuvre des methodes chimiques, physiques et electrochimiques et nous avons ainsi pu mettre en evidence le processus de l'attaque oxydante. La particule de noir de carbone est un ensemble spherique constitue essentiellement de carbone engage dans des domaines amorphes et dans des domaines cristallins. L'attaque oxydante se fait surtout aux depens des parties amorphes qui entourent les cristallites. Si l'attaque est suffisamment poussee, les cristallites sont liberes ce qui se traduit par l'effondrement de la particule. C'est la conjugaison de la microscopie electronique, des rayons X, de la methode d'absorption d'azote B.E.T. et des infra-rouge qui ont permis d'etablir ce schema de l'attaque oxydante. Sur le plan des analyses chimiques, nous avons confirme la presence de fonctions carboxyles, hydroxyles et quinones a la surface de la particule de noir de carbone oxyde et avons pu les doser. Une des methodes de dosage quantitative des

  18. One-Pot Two-Step Multicomponent Process of Indole and Other Nitrogenous Heterocycles or Amines toward α-Oxo-acetamidines.

    Martinez-Ariza, Guillermo; McConnell, Nicholas; Hulme, Christopher

    2016-04-15

    A cesium carbonate promoted three-component reaction of N-H containing heterocycles, primary or secondary amines, arylglyoxaldehydes, and anilines is reported. The key step involves a tandem sequence of N-1 addition of a heterocycle or an amine to preformed α-iminoketones, followed by an air- or oxygen-mediated oxidation to form α-oxo-acetamidines. The scope of the reaction is enticingly broad, and this novel methodology is applied toward the synthesis of various polycyclic heterocycles.

  19. Influence de l'irrigation sur le rendement et sur la qualité des raisins

    J. Cerny

    1968-12-01

     Le travail présenté résume les résultats de l'expérience avec l'irrigation supplémentaire de la vigne dans le domaine sec du Sud de la Moravie ainsi que son influence sur le rendement et la qualité des raisins.

  20. Two food-borne heterocyclic amines: Metabolism and DNA adduct formation of amino-alpha-carbolines

    Frederiksen, Hanne

    2005-01-01

    or proteins of animal or vegetable origin, furthermore they are found in many cooked foods, such as fish, meat, and chicken. The specific mutagenicity of the amino-a-carbolines are lower in the Ames Salmonella assay than other heterocyclic amines, but in rodent studies the carcinogenicity of the aminoa, alpha......The amino-alpha-carbolines 2-amino-9H-pyrido[2,3-b]indole (A alpha C) and 2-amino-3-methyl-9H-pyrido-[2,3-b]indole (MeA alpha C) are two mutagenic and carcinogenic heterocyclic amines formed during ordinary cooking. Amino-alpha-carbolines can be formed in model systems by pyrolyzing tryptophan...

  1. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan

    2008-02-04

    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  2. Synthesis of heterocycles via transition-metal-catalyzed hydroarylation of alkynes.

    Yamamoto, Yoshihiko

    2014-03-07

    Transition-metal (TM)-catalyzed hydroarylation reactions of alkynes have received much attention, because they enable the net insertion of alkyne C-C triple bonds into C-H bonds of aromatic precursors, resulting in regio- and stereo-selective formation of synthetically useful arylalkenes. Taking advantage of this feature, TM-catalyzed alkyne hydroarylations have been successfully used for the synthesis of heterocycles. TM-catalyzed alkyne hydroarylations can be classified into three major categories depending on the type of reaction and precursors involved: (1) palladium-catalyzed reductive Heck reactions of alkynes with aryl halides, (2) TM-catalyzed conjugate arylation reactions of activated alkynes with arylboronic acids, and (3) TM-catalyzed aromatic C-H alkenylations with alkynes. This review surveys heterocycle synthesis via TM-catalyzed hydroarylation of alkynes according to the above classification, with an emphasis on the scope and limitations, as well as the underlying mechanisms.

  3. Anaerobic biodegradation of halogenated and nonhalogenated N-, s-, and o-heterocyclic compounds in aquifer slurries

    Adrian, Neal R.; Suflita, Joseph M.

    1994-01-01

    The fate of several halogenated and nonhalogenated heterocyclic compounds in anoxic aquifer slurries was investigated Substrate depletion and methane formation were monitored in serum bottle incubations by HPLC and GC, respectively Pyridine, pyrimidine, thiophene, and furan were not mineralized following an 11-month incubation, but the corresponding carboxylated or oxygenated compounds were That is, >74% of the theoretically expected amount of methane was recovered from nicotinic acid, uracil, or 2-furoic acid Chlorinated derivatives, like 2 chloro- or 6-chloronicotinic acid, as well as 4 chloro- and 5-chlorouracil resisted mineralization However, 5-bromouracil was reductively dehalogenated to stoichiometric amounts of uracil, whereas 2-chloropyrimidine was metabolized to a more polar unidentified compound that resisted further anaerobic biodegradation Microorganisms acclimated to 5-bromouracil were unable to transform 4 chloro or 5 chlorouracil These findings illustrate how the structure of heterocyclic contaminants influences their susceptibility to anaerobic decay

  4. Mn(III)-initiated facile oxygenation of heterocyclic 1,3-dicarbonyl compounds.

    Rahman, Md Taifur; Haque, Md Aminul; Igarashi, Hikaru; Nishino, Hiroshi

    2011-11-16

    The Mn(III)-initiated aerobic oxidation of heterocyclic 1,3-dicarbonyl compounds, such as 4-alkyl-1,2-diphenylpyrazolidine-3,5-diones, 1,3-dialkylpyrrolidine-2,4-diones, 3-alkyl-1,5-dimethylbarbituric acids, and 3-butyl-4-hydroxy-2-quinolinone gave excellent to good yields of the corresponding hydroperoxides, which were gradually degraded by exposure to the metal initiator after the reaction to afford the corresponding alcohols. The synthesis of 30 heterocyclic 1,3-dicarbonyl compounds, the corresponding hydroperoxides and the 10 alcohols, their characterization, and the limitations of the procedure are described. In addition, the mechanism of the hydroperoxidation and the redox decomposition of the hydroperoxides are discussed.

  5. Interpretation of electronic spectra of ruthenium nitroso complexes with N-heterocyclic ligands

    Sizova, O.V.; Ivanova, N.V.; Lyubimova, O.O.; Nikol'skij, A.B.

    2004-01-01

    Relaying on ab initio and semiempirical CINDO/CI calculations of free ligands L and complexes trans-[Ru(NO)(NH 3 ) 4 (L)] 3+ (L=pyridine, pyrazine, nicotinamide, l-histidine, imidazole), electronic absorption spectra of nitroso complexes with nitrogen-containing heterocyclic ligands L have been analyzed. Spectral manifestations of strong covalent bond Ru-NO was pointed out and the conclusion was made about advisability of presentation of Ru and NO oxidation states in grouping RuNO 3+ as Ru(III) and NO 0 . Introduction of nitroso group into inner coordination sphere of Ru(II) complexes with nitrogen-containing heterocyclic ligands results in essential rearrangement of the entire structure and deprives ligands L of their ability to manifest chromophore properties [ru

  6. Abiotic synthesis of purines and other heterocyclic compounds by the action of electrical discharges

    Yuasa, S.; Flory, D.; Basile, B.; Oro, J.

    1984-01-01

    The synthesis of purines and pyrimidines using Oparin-Urey-type primitive earth atmospheres has been demonstrated by reacting methane, ethane, and ammonia in electrical discharges. Adenine, guaine, 4-aminoimidazole-5-carboxamide (AICA), and isocytosine have been identified by UV spectrometry and paper chromatography as the products of the reaction. The total yields of the identified heterocyclic compounds are 0.0023 percent. It is concluded that adenine synthesis occurs at a much lower concentration of hydrogen cyanide than has been shown by earlier studies. Pathways for the synthesis of purines from hydrogen cyanide are discussed, and a comparison of the heterocyclic compounds that have been identified in meteorites and in prebiotic reactions is presented.

  7. Far IR spectra of Th(IV) halide complexes of some heterocyclic bases

    Srivastava, A.K.; Agarwal, R.K.; Srivastava, M.; Kapoor, V.; Srivastava, T.N.

    1981-01-01

    The synthesis and IR spectra of Th(IV) perchlorato, nitrato and thiocyanato complexes of some heterocyclic bases have been reported. Halogens are common ligands in coordination chemistry forming coordinate bonds with metals readily. Metal halogen (M-X) stretching bands show a strong absorption in the far-IR region. Very little information is available on Th-X stretching frequencies. In the present communication, adducts of Th(IV) halide with certain nitrogen heterocyclic bases such as pyridine, α-picoline, 2-amino pyridine, 2:4-lutidine, 2:6-lutidine, quinoline, 2,2'-bipyridine and 1,10-phenanthroline were synthesised and characterised. Experimental details are given. Results are presented and discussed. (author)

  8. Reaction of vanadocene and its monochloride with salts of nitrogen-containing heterocycles

    Gordetsov, A.S.; Pereshein, V.V.; Lyatyaeva, V.N.; Mar'in, V.P.; Rukevich, OS.; Zakharova, E.S.

    1985-01-01

    The reaction of bis(eta 5 -cyclopentadienyl) vanadium (Cp 2 V) and its monochloride with diallyl isocyanurates of Ag and alkali metals and with Ag salt of succinimide is used for preparing almost inaccessible Cp 2 V-substituted nitrogen-containing heterocycles. The reactions have been performed in toluene in an evacuated ampoule at room temperature and at 120-130 deg C in case of diallyl isocyanurates of alkali metals. Reaction yields element analysis data, DTA, IR spectra and ESR spectra. Cp 2 V easily reduces Ag from its salts with nitrogen-containing heterocycles oxidizing with production of V(3) sandwich derivatives In exchange reactions of Cp 2 VCl with diallyl isocyanurate salts of alkali metals and silver Cp 2 V-diallyl isocyanurate with an oxo-structure is prosduced as well. The produced AgCl subsequently oxidizers Cp 2 VCl up to Cp 2 VCl 2

  9. N-heterocyclic carbene complexes of silver and gold as novel tools against breast cancer progression.

    Saturnino, Carmela; Barone, Ines; Iacopetta, Domenico; Mariconda, Annaluisa; Sinicropi, Maria Stefania; Rosano, Camillo; Campana, Antonella; Catalano, Stefania; Longo, Pasquale; Andò, Sebastiano

    2016-12-01

    Metal carbenic complexes have received considerable attention in both the catalysis and biological fields for their potential applications in cancer and antimicrobial therapies. A small series of new silver and gold N-heterocyclic carbene complexes has been designed and synthesized. Among the tested complexes, one compound was particularly active in inhibiting anchorage-dependent and -independent breast cancer proliferation, and inducing cell apoptosis via a mitochondria-related process. The antitumor activity was associated to the transcriptional activation of the tumor suppressor gene p53 in an Sp1-dependent manner, as evidenced by biological and docking studies. Our results highlight the importance and the versatility of N-heterocyclic carbene complexes of gold and silver as useful tools against breast cancer progression.

  10. Synthesis and Radiolabeling of Modified Peptides Attached to Heterocyclic Rings and Their Possible Medical Applications

    Shams El-Din, H.A.A.

    2012-01-01

    Keeping in mind the pharmacological potential of heterocyclic rings as well as the advantage of biodegradability and biocompatibility of amino acids/peptides, in this thesis we were prompted for the following: 1. Synthesis of novel dipeptide derivatives coupled with different heterocyclic rings (pyridine, 1,2,4-triazol-pyridine, 1,3,4-oxadiazolpyridine and tetrazol-pyridine rings). 2. Characterization of the synthesized compounds on the basis of their spectral data (IR, Mass and 1 H-NMR spectra). 3. Study their antimicrobial activity as one of their expected biological activities. 4. Study the radioiodination of some synthesized dipeptide derivatives. 5. Study the biodistribution of the radiolabeled compounds in normal mice as preliminary studies for the possibility of using them as agents for imaging and treatment.

  11. Mn(III-Initiated Facile Oxygenation of Heterocyclic 1,3-Dicarbonyl Compounds

    Md. Aminul Haque

    2011-11-01

    Full Text Available The Mn(III-initiated aerobic oxidation of heterocyclic 1,3-dicarbonyl compounds, such as 4-alkyl-1,2-diphenylpyrazolidine-3,5-diones, 1,3-dialkylpyrrolidine-2,4-diones, 3-alkyl-1,5-dimethylbarbituric acids, and 3-butyl-4-hydroxy-2-quinolinone gave excellent to good yields of the corresponding hydroperoxides, which were gradually degraded by exposure to the metal initiator after the reaction to afford the corresponding alcohols. The synthesis of 30 heterocyclic 1,3-dicarbonyl compounds, the corresponding hydroperoxides and the 10 alcohols, their characterization, and the limitations of the procedure are described. In addition, the mechanism of the hydroperoxidation and the redox decomposition of the hydroperoxides are discussed.

  12. Basic deuteroexchange in complexes of transition metals with nitrogen-containing aromatic heterocycles

    Tupitsyn, I.F.

    1986-01-01

    A study was made of the kinetics of deuteroexchange in the methyl group in complexes of one metal [nickel(II)] with different methyl-substituted aromatic heterocycles and in isostructural complexes of one ligand (2-methylquinoline) with different central metal atoms (Mn 2+ , Ni 2+ , Cu 2+ , Zn 2+ ). The order in which the structures of the ligands influence the rate of deuteroexchange in the complexes does not correspond qualitatively with the order of increase in the rate of deuteroexchange in the noncoordinated ligands. The rate of deuteroexchange is only weakly influenced by change in the identity of the metal complex former. A deuteroexchange mechanism is proposed and discussed. A structure arising in the course of the exchange process with transfer of electron density from the heterocyclic ligand to the metal ion forms the transition state of the reaction

  13. Basic deuteroexchange in transition metal complexes with nitrogen-containing aromatic heterocycles

    Tupitsyn, I.F.

    1986-01-01

    Kinetics of deuteroexchange in the methyl group of nitrate complexes of a metal - nickel (2) - with different methyl-substituted aromatic heterocycles and isostructural complexes of a ligand - 2 - methyl quinoline - with different central metal atoms (Mn(2), Ni(2), Cu(2), Zn(2)) is studied. Series for influence of ligand structure on deuteroexchange rate in complexes doesn't correspond qualitatively to series for deuteroexchange rate increase in noncoordinated ligands. Deuteroexchange rate is weakly subjected to influence of exchange in metal-complexing agent. Deuteroexchange mechanism is suggested and discussed. According to this mechanism the structure developed in the course of the exchange process with electron density transfer from the heterocyclic ligand to a metal ion is a transition state of the reaction

  14. Decisive Interactions between the Heterocyclic Moiety and the Cluster Observed in Polyoxometalate-Surfactant Hybrid Crystals

    Saki Otobe

    2015-04-01

    Full Text Available Inorganic-organic hybrid crystals were successfully obtained as single crystals by using polyoxotungstate anion and cationic dodecylpyridazinium (C12pda and dodecylpyridinium (C12py surfactants. The decatungstate (W10 anion was used as the inorganic component, and the crystal structures were compared. In the crystal comprising C12pda (C12pda-W10, the heterocyclic moiety directly interacted with W10, which contributed to a build-up of the crystal structure. On the other hand, the crystal consisting of C12py (C12py-W10 had similar crystal packing and molecular arrangement to those in the W10 crystal hybridized with other pyridinium surfactants. These results indicate the significance of the heterocyclic moiety of the surfactant to construct hybrid crystals with polyoxometalate anions.

  15. Nitrogen-rich heterocycles as reactivity retardants in shocked insensitive explosives.

    Manaa, M Riad; Reed, Evan J; Fried, Laurence E; Goldman, Nir

    2009-04-22

    We report the first quantum-based multiscale simulations to study the reactivity of shocked perfect crystals of the insensitive energetic material triaminotrinitrobenzene (TATB). Tracking chemical transformations of TATB experiencing overdriven shock speeds of 9 km/s for up to 0.43 ns and 10 km/s for up to 0.2 ns reveal high concentrations of nitrogen-rich heterocyclic clusters. Further reactivity of TATB toward the final decomposition products of fluid N(2) and solid carbon is inhibited due to the formation of these heterocycles. Our results thus suggest a new mechanism for carbon-rich explosive materials that precedes the slow diffusion-limited process of forming the bulk solid from carbon clusters and provide fundamental insight at the atomistic level into the long reaction zone of shocked TATB.

  16. Turistas hispanohablantes en Corea del Sur

    Arroyo Herrera, Javier

    2016-01-01

    Dada la evolución económica que ha experimentado en los últimos años y el aumento de las llegadas de turistas internacionales debido a fenómenos como el Hallyu, Corea del Sur se está convirtiendo en un foco de atención turística que requiere de estudios para conocer mejor su turismo y la importancia que la cultura popular supone para éste. La presente investigación recopila los elementos más destacables del turismo surcoreano y demuestra la influencia que la „ola coreana‟ provoca en sus segui...

  17. Meat Consumption, Heterocyclic Amines, and Colorectal Cancer Risk: The Multiethnic Cohort Study

    Ollberding, Nicholas J.; Wilkens, Lynne R.; Henderson, Brian E.; Kolonel, Laurence N.; Le Marchand, Loïc

    2012-01-01

    Greater consumption of red and processed meat has been associated with an increased risk of colorectal cancer in several recent meta-analyses. Heterocyclic amines (HCAs) have been hypothesized to underlie this association. In this prospective analysis conducted within the Multiethnic Cohort Study, we examined whether greater consumption of total, red, or processed meat was associated with the risk of colorectal cancer among 165,717 participants who completed a detailed food frequency question...

  18. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    Falivene, Laura

    2016-12-26

    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise surprising experimental results. In this review, the main conclusions from recent literature are discussed, with the aim to offer a vision of the potential of theoretical analyses of NMR properties.

  19. Gold(I-catalyzed domino cyclization for the synthesis of polyaromatic heterocycles

    Mathieu Morin

    2013-11-01

    Full Text Available Gold(I complexes have emerged as powerful and useful catalysts for the formation of new C–C, C–O and C–N bonds. Taking advantage of the specificity of [IPrAuNCMe][SbF6] complexes to favor the 5-exo-dig cyclization over the 6-endo-dig pathway, we report a high yielding and efficient method to generate substituted polyaromatic heterocycles under remarkably mild reaction conditions.

  20. Application of heterocyclic aldehydes as components in Ugi–Smiles couplings

    Katelynn M. Mason

    2016-09-01

    Full Text Available Efficient one-pot Ugi–Smiles couplings are reported for the use of furyl-substituted aldehyde components. In the presence of these heterocyclic aldehydes, reactions tolerated variations in amine components and led to either isolated N-arylamide Ugi–Smiles adducts or N-arylepoxyisoindolines, products of tandem Ugi–Smiles Diels–Alder cyclizations, in moderate yields. A thienyl-substituted aldehyde was also a competent component for Ugi–Smiles adduct formation.

  1. Asymmetric Reduction of tert-Butanesulfinyl Ketimines by N-Heterocyclic Carbene Boranes.

    Liu, Tao; Chen, Ling-yan; Sun, Zhihua

    2015-11-20

    N-heterocyclic carbene borane (NHC-borane) based on a triazole core is demonstrated for the first time to be efficient for reduction of a variety of tert-butanesulfinyl ketimines. Up to 95% yield and up to >99% diastereomeric excess were achieved. NHC-borane exhibited excellent activities that are more efficient than or comparable to commonly used reductive reagents such as NaBH4, NaBH3CN, l-selectride, Ru catalyst, or BH3-THF.

  2. Antioxidant Activity of Novel Fused Heterocyclic Compounds Derived from Tetrahydropyrimidine Derivative.

    Salem, Marwa Sayed; Farhat, Mahmoud; Errayes, Asma Omar; Madkour, Hassan Mohamed Fawzy

    2015-01-01

    6-(Benzo[d][1,3]dioxol-5-yl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile has been utilized for synthesis of the fused heterocyclic compounds namely thiazolopyrimidines, tetrazolopyrimidine, pyrimidoquinazoline, pyrimidothiazolopyrimidine, pyrimidothiazolotriazine and pyrrolothiazolopyrimidine derivatives. The newly synthesized compounds were characterized by IR, (1)H-NMR, (13)C-NMR, and mass spectral data. Antioxidant activities of all synthesized compounds were investigated.

  3. Heterocyclization reaction of 4-(2-Methylaziridin-1-yl)-3-ureidobenzotrifluorides under appel's conditions

    Cho, Hyun In; Lee, Kee Jung

    2003-01-01

    The reaction of 4-(2-Methylaziridin-1-yl)-3-ureidobenzotrifluorides 4 with triphenylphosphine, carbon tetrachloride, and triethylamine (Appel's condition) led to the corresponding carbodiimides 5, which underwent intramolecular cycloaddition reaction with aziridine under the reaction condition to give the benzimidazole-fused heterocycles, 2.3-dihydro-1H-imidazo(1,2-a)benzimidazoles 8 and 12,13-dihydro-5H-benzimidazo(2,3-b)(1,3)benzodizzepines 9

  4. Investigation of the structure and properties of heterocyclic compounds and their complexes

    Shejnker, V.N.; Troilina, V.S.; Merinova, E.G.; Garnovskij, A.D.; Osipov, O.A.

    1988-01-01

    Complexing of acetyl derivatives of azoles with iodine and bromine iodide is investigated using UV-spectroscopy and dipole moment methods. In bimolecular complexes σ-acceptor coordination occurs by heterocycle pyridine type nitrogen atom and is not accompanied by the ligand conformation change. The complex stability increases in agreement with azole basicity. For N-acetyltriazole ligand, conformation reversal occurs in its trimolecular complex with IBr

  5. Regiospecificity in the heterocyclization of b-oxonitriles to 5-substituted 4-oxothiazolidine derivatives

    PETER STEEL

    2003-05-01

    Full Text Available A study on the regiospecificity of the base-catalyzed reaction of activated b-oxonitriles 1 with diethyl mercaptosuccinate affording the title compounds 3 is reported. Other competitive heterocyclic products, that is 4-oxo-1,3-thiazinanes 4, derivatives of tetrahydrothiophene 5 and/or thiacyclohexane 6 which on the grounds of mechanistic considerations could be formed, were not observed. Spectroscopic and experimental evidence, together with theoretical considerations, provides a reasonable explanation for the observed regiospecificity.

  6. The design and synthesis of novel spirocyclic heterocyclic sulfone ROMK inhibitors as diuretics.

    Chobanian, Harry R; Guo, Yan; Pio, Barbara; Tang, Haifeng; Teumelsan, Nardos; Clements, Matthew; Frie, Jessica; Ferguson, Ronald; Guo, Zach; Thomas-Fowlkes, Brande S; Felix, John P; Liu, Jessica; Kohler, Martin; Priest, Birgit; Hampton, Caryn; Pai, Lee-Yuh; Corona, Aaron; Metzger, Joseph; Tong, Vincent; Joshi, Elizabeth M; Xu, Ling; Owens, Karen; Maloney, Kevin; Sullivan, Kathleen; Pasternak, Alexander

    2017-02-15

    A spirocyclic class of ROMK inhibitors was developed containing a structurally diverse heterocyclic sulfone moiety and spirocyclic core starting from lead 1. These compounds not only displayed exquisite ROMK potency but significantly improved selectivity over hERG. The lead compounds were found to have favorable pharmacokinetic properties and displayed robust diuretic, natriuretic and blood pressure lowering effects in spontaneously hypertensive rats. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Bimacrocyclic concave N-heterocyclic carbenes (NHCs): synthesis, structure, and application in catalyses

    Lüning , Ulrich; Winkelmann , Ole

    2009-01-01

    Abstract Imidazolinium moieties have been incorporated into bimacrocycles to generate precursors for concave N-heterocyclic carbenes (NHCs). Starting from 2-nitroresorcinol and alkenols, symmetric concave imidazolinium salts 1 were obtained. Bimacrocyclization was achieved via ring closing metathesis (RCM). In an analogous fashion, axially chiral concave imidazolinium salts 2 were obtained by using a naphthalene bridgehead devoid of local C2-symmetry. The concave NHCs derived from ...

  8. Pyridynes and indolynes as building blocks for functionalized heterocycles and natural products.

    Goetz, Adam E; Shah, Tejas K; Garg, Neil K

    2015-01-04

    Heterocyclic arynes, or hetarynes, have been studied for over 100 years. However, challenges associated with observing these reactive species, as well as developing synthetically useful methods for their generation and trapping, have limited their use. This review provides a brief historical perspective on the field of hetarynes, in addition to a discussion of pyridyne and indolyne methodologies. Moreover, this review highlights the use of pyridynes, indolynes, and related strained intermediates in natural product synthesis.

  9. Formation and ecotoxicity of N-heterocyclic compounds on ammoxidation of mono- and polysaccharides.

    Klinger, Karl Michael; Liebner, Falk; Fritz, Ines; Potthast, Antje; Rosenau, Thomas

    2013-09-25

    Ammoxidation of technical lignins under mild conditions is a suitable approach to artificial humic substances. However, carbohydrates as common minor constituents of technical lignins have been demonstrated to be a potential source of N-heterocyclic ecotoxic compounds. Ethyl acetate extracts of ammoxidation mixtures of the monosaccharides glucose and xylose exhibited considerable growth inhibiting activity in the OECD 201 test, with 4-methyl-1H-imidazole, 4-(hydroxymethyl)-1H-imidazole, and 3-hydroxypyridine being the most active compounds. The amount of N-heterocyclic compounds formed at moderate ammoxidation conditions (70 °C, 0.2 MPa O2, 3 h) was significantly lower for the polysaccharides cellulose and xylan (16-30 μg/g of educt) compared to glucose (15.4 mg). Ammoxidation at higher temperature is not recommendable for carbohydrate-rich materials as much higher amounts of N-heterocyclic compounds were formed from both monosaccharides (100 °C: 122.4-160.5 mg/g of educt) and polysaccharides (140 °C: 5.52-16.03 mg/g of educt).

  10. Theoretical study of ionization and one-electron oxidation potentials of N-heterocyclic compounds.

    Sviatenko, Liudmyla K; Gorb, Leonid; Hill, Frances C; Leszczynski, Jerzy

    2013-05-15

    A number of density functionals was utilized to predict gas-phase adiabatic ionization potentials (IPs) for nitrogen-rich heterocyclic compounds. Various solvation models were applied to the calculation of difference in free energies of solvation of oxidized and reduced forms of heterocyclic compounds in acetonitrile (AN) for correct reproduction of their standard oxidation potentials. We developed generally applicable protocols that could successfully predict the gas-phase adiabatic ionization potentials of nitrogen-rich heterocyclic compounds and their standard oxidation potentials in AN. This approach is supported by a MPW1K/6-31+G(d) level of theory which uses SMD(UA0) approximation for estimation of solvation energy of neutral molecules and PCM(UA0) model for ionized ones. The mean absolute derivation (MAD) and root mean square error (RMSE) of the current theoretical models for IP are equal to 0.22 V and 0.26, respectively, and for oxidation potentials MAD = 0.13 V and RMSE = 0.17. Copyright © 2013 Wiley Periodicals, Inc.

  11. A comprehensive evaluation of the toxicology of cigarette ingredients: heterocyclic nitrogen compounds.

    Coggins, Christopher R E; Merski, Jerome A; Oldham, Michael J

    2011-06-01

    Three heterocyclic nitrogen compounds, 2,3-diethylpyrazine (DEP), 2,3,5,6-tetramethylpyrazine (TMP), and 2-acetyl pyridine (AP), are naturally present in tobacco and are also added to tobacco as flavor ingredients. A battery of tests was used to compare the toxicity of mainstream smoke from experimental cigarettes containing the three heterocyclic nitrogen compounds added individually at three different levels. The lowest target inclusion level of the ingredient was 10 ppm, and the highest was 10,000 ppm. Smoke from experimental and control cigarettes was evaluated in analytical smoke chemistry, in vitro cytotoxicity, and mutagenicity assays. The cigarettes with added DEP produced some minor (approximately 10%) changes in smoke chemistry when compared with the cigarettes containing no DEP. Smoke chemistry was effectively unchanged by the addition of either AP or TMP. Cytotoxicity, assessed by the neutral red uptake assay using both gas-vapor and particulate phases of smoke, was unaffected by the addition of any of the test ingredients. Mutagenicity, assessed in five strains of Salmonella treated with mainstream cigarette smoke condensate, also was unaffected by any of the test ingredients. Despite the exaggerated ingredient levels relative to commercial-use levels, there was a lack of a toxicological response for the three heterocyclic nitrogen compounds in the test systems used.

  12. Auspicious role of the steroidal heterocyclic derivatives as a platform for anti-cancer drugs.

    Tantawy, Mohamed A; Nafie, Mohamed S; Elmegeed, Gamal A; Ali, Ibrahim A I

    2017-08-01

    Steroids are polycyclic compounds that have a wide range of biological activities. They are bio-synthesized from cholesterol through a series of enzyme-mediated transformations, so they are highly lipophilic and readily enter most cells to interact with intracellular receptors, making them ideal vehicles for targeting a broad array of pathologies. New curative agents for cancers have been developed from several steroidal derivatives. Some biologically important properties of modified steroids are dependent on structural features of the steroid moiety and their side chains. Therefore, chemical derivatization of steroids provides a way to modify their function, and many structure-activity relationships have been confirmed by such synthetic modifications. Several studies demonstrate that steroidal heterocyclic derivatives can be effective in the prevention and treatment of many types of hormone-dependent cancers. The present review is a concise report on steroidal heterocyclic derivatives, with special emphasis on steroid heterocyclic derivatives with 5 membered rings or six-membered rings having interesting therapeutic potential as enzyme inhibitors and cytotoxic drugs to be used as candidates for anti-cancer drug development. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Formation of Haloacetonitriles, Haloacetamides, and Nitrogenous Heterocyclic Byproducts by Chloramination of Phenolic Compounds.

    Nihemaiti, Maolida; Le Roux, Julien; Hoppe-Jones, Christiane; Reckhow, David A; Croué, Jean-Philippe

    2017-01-03

    The potential formation of nitrogenous disinfection byproducts (N-DBPs) was investigated from the chloramination of nitrogenous and non-nitrogenous aromatic compounds. All molecules led to the formation of known N-DBPs (e.g., dichloroacetonitrile, dichloroacetamide) with various production yields. Resorcinol, a major precursor of chloroform, also formed di/trichloroacetonitrile, di/trichloroacetamide, and haloacetic acids, indicating that it is a precursor of both N-DBPs and carbonaceous DBPs (C-DBPs) upon chloramination. More detailed experiments were conducted on resorcinol to understand N-DBPs formation mechanisms and to identify reaction intermediates. Based on the accurate mass from high resolution Quadrupole Time-of-Flight GC-MS (GC-QTOF) and fragmentation patterns from electronic impact and positive chemical ionization modes, several products were tentatively identified as nitrogenous heterocyclic compounds (e.g., 3-chloro-5-hydroxy-1H-pyrrole-2-one with dichloromethyl group, 3-chloro-2,5-pyrroledione). These products were structurally similar to the heterocyclic compounds formed during chlorination, such as the highly mutagenic MX (3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone) or halogenated pyrroles. To our knowledge, this is the first time that the formation of halogenated nitrogenous heterocyclic compounds is reported from chloramination process. The formation of these nitrogenous byproducts during chloramination might be of concern considering their potential toxicity.

  14. Recent advances in novel heterocyclic scaffolds for the treatment of drug-resistant malaria.

    Kumar, Sahil; Singh, Rajesh K; Patial, Babita; Goyal, Sachin; Bhardwaj, T R

    2016-01-01

    Malaria is a major public health problem all over the world, particularly in tropical and subtropical countries due to the development of resistance and most deadly infection is caused by Plasmodium falciparum. There is a direct need for the discovery of new drugs with unique structures and mechanism of action to treat sensitive and drug-resistant strains of various plasmodia for radical cure of this disease. Traditional compounds such as quinine and related derivatives represent a major source for the development of new drugs. This review presents recent modifications of 4-aminoquinoline and 8-aminoquinolone rings as leads to novel active molecules which are under clinical trials. The review also encompasses the other heterocyclic compounds emerged as potential antimalarial agents with promising results such as acridinediones and acridinone analogues, pyridines and quinolones as antimalarials. Miscellaneous heterocyclics such as tetroxane derivatives, indole derivatives, imidazolopiperazine derivatives, biscationic choline-based compounds and polymer-linked combined antimalarial drugs are also discussed. At last brief introduction to heterocyclics in natural products is also reviewed. Most of them have been under clinical trials and found to be promising in the treatment of drug-resistant strains of Plasmodium and others can be explored for the same purpose.

  15. Effects of nitro-heterocyclic derivatives against Leishmania (Leishmania) infantum promastigotes and intracellular amastigotes.

    Petri e Silva, Simone Carolina Soares; Palace-Berl, Fanny; Tavares, Leoberto Costa; Soares, Sandra Regina Castro; Lindoso, José Angelo Lauletta

    2016-04-01

    Leishmaniasis is an overlooked tropical disease affecting approximately 1 million people in several countries. Clinical manifestation depends on the interaction between Leishmania and the host's immune response. Currently available treatment options for leishmaniasis are limited and induce severe side effects. In this research, we tested nitro-heterocyclic compounds (BSF series) as a new alternative against Leishmania. Its activity was measured in Leishmania (Leishmania) infantum promastigotes and intracellular amastigotes using MTT colorimetric assay. Additionally, we assessed the phosphatidylserine exposure by promastigotes, measured by flow cytometry, as well as nitric oxide production, measured by Griess' method. The nitro-heterocyclic compounds (BSF series) showed activity against L. (L.) infantum promastigotes, inducting the phosphatidylserine exposition by promastigotes, decreasing intracellular amastigotes and increasing oxide nitric production. The selectivity index was more prominent to Leishmania than to macrophages. Compared to amphotericin b, our compounds presented higher IC50, however the selectivity index was more specific to parasite than to amphotericin b. In conclusion, these nitro-heterocyclic compounds showed to be promising as an anti-Leishmania drug, in in vitro studies. Copyright © 2016 Elsevier Inc. All rights reserved.

  16. Adsorption Characteristics of DNA Nucleobases, Aromatic Amino Acids and Heterocyclic Molecules on Silicene and Germanene Monolayers

    Hussain, Tanveer

    2017-09-14

    Binding of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules on two-dimensional silicene and germanene sheets have been investigated for the application of sensing of biomolecules using first principle density functional theory calculations. Binding energy range for nucleobases, amino acids and heterocyclic molecules with both the sheets have been found to be (0.43-1.16eV), (0.70-1.58eV) and (0.22-0.96eV) respectively, which along with the binding distances show that these molecules bind to both sheets by physisorption and chemisorption process. The exchange of electric charges between the monolayers and the incident molecules has been examined by means of Bader charge analysis. It has been observed that the introduction of DNA/RNA nucleobases, aromatic amino acids and heterocyclic molecules alters the electronic properties of both silicene and germanene nano sheets as studied by plotting the total (TDOS) and partial (PDOS) density of states. The DOS plots reveal the variation in the band gaps of both silicene and germanene caused by the introduction of studied molecules. Based on the obtained results we suggest that both silicene and germanene monolayers in their pristine form could be useful for sensing of biomolecules.

  17. Impact of environmental exposures on the mutagenicity/carcinogenicity of heterocyclic amines

    Felton, James S; Knize, Mark G; Bennett, L Michelle; Malfatti, Michael A; Colvin, Michael E; Kulp, Kristen S

    2004-05-20

    Carcinogenic heterocyclic amines are produced from overcooked foods and are highly mutagenic in most short-term test systems. One of the most abundant of these amines, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), induces breast, colon and prostate tumors in rats. Human dietary epidemiology studies suggest a strong correlation between either meat consumption or well-done muscle meat consumption and cancers of the colon, breast, stomach, lung and esophagus. For over 20 years our laboratory has helped define the human exposure to these dietary carcinogens. In this report we describe how various environmental exposures may modulate the risk from exposure to heterocyclic amines, especially PhIP. To assess the impact of foods on PhIP metabolism in humans, we developed an LC/MS/MS method to analyze the four major PhIP urinary metabolites following the consumption of a single portion of grilled chicken. Adding broccoli to the volunteers' diet altered the kinetics of PhIP metabolism. At the cellular level we have found that PhIP itself stimulates a significant estrogenic response in MCF-7 cells, but even more interestingly, co-incubation of the cells with herbal teas appear to enhance the response. Numerous environmental chemicals found in food or the atmosphere can impact the exposure, metabolism, and cell proliferation response of heterocyclic amines.

  18. Impact of environmental exposures on the mutagenicity/carcinogenicity of heterocyclic amines

    Felton, James S.; Knize, Mark G.; Bennett, L. Michelle; Malfatti, Michael A.; Colvin, Michael E.; Kulp, Kristen S.

    2004-01-01

    Carcinogenic heterocyclic amines are produced from overcooked foods and are highly mutagenic in most short-term test systems. One of the most abundant of these amines, 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), induces breast, colon and prostate tumors in rats. Human dietary epidemiology studies suggest a strong correlation between either meat consumption or well-done muscle meat consumption and cancers of the colon, breast, stomach, lung and esophagus. For over 20 years our laboratory has helped define the human exposure to these dietary carcinogens. In this report we describe how various environmental exposures may modulate the risk from exposure to heterocyclic amines, especially PhIP. To assess the impact of foods on PhIP metabolism in humans, we developed an LC/MS/MS method to analyze the four major PhIP urinary metabolites following the consumption of a single portion of grilled chicken. Adding broccoli to the volunteers' diet altered the kinetics of PhIP metabolism. At the cellular level we have found that PhIP itself stimulates a significant estrogenic response in MCF-7 cells, but even more interestingly, co-incubation of the cells with herbal teas appear to enhance the response. Numerous environmental chemicals found in food or the atmosphere can impact the exposure, metabolism, and cell proliferation response of heterocyclic amines

  19. Regard sur les Lazarets en Terre Canadienne

    Jean Milot

    2008-01-01

    Full Text Available Puisant dans les nombreuses références qu’offrent les publications médicales canadiennes du milieu du XIXe siècle à nos jours, l’auteur fait découvrir l’existence de lazarets en terre canadienne, décrit l’impact de la maladie sur les conditions vie des lépreux qui y étaient confinés et en souligne les contrecoups tant sur le plan physique et psychologique que social. Il présente un bref aperçu de la maladie, ses symptômes, ses signes ainsi que ses complications oculaires et rappelle les premiers moyens thérapeutiques à base d’huile de chaulmoogra introduits dans la colonie de Tracadie vers 1901. Il illustre son propos en évoquant la vie dans les lazarets de l’île de Sheldrake (1844–1848 et de Tracadie (1848–1965 au Nouveau-Brunswick, puis dans ceux des îles D’Arcy (1891–1924 et de Bentinck (1924–1957 en Colombie-Britannique.

  20. Effect of cooking time and temperature on the heterocyclic amine content of fried beef patties.

    Knize, M G; Dolbeare, F A; Carroll, K L; Moore, D H; Felton, J S

    1994-07-01

    The mutagenic heterocyclic amines 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) and 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (DiMeIQx) were measured in ground-beef patties fried at 150, 190 and 230 degrees C for 2-10 min on each side. Heterocyclic amines were purified using solid-phase extraction and analysed by HPLC. Recovery-corrected amounts of each heterocyclic amine were determined by the method of standard addition based on spiked samples with recoveries ranging from 40 to 70%. Mutagenic activity measured by the Ames/Salmonella test was determined for each sample. The amounts of MeIQx, PhIP, DiMeIQx and IQ increased with time and temperature of cooking. 3-Amino-1,4-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P-2) and 2-amino-9H-pyrido[2,3-b]indole (A alpha C) were not detected in any sample. The mutagenic activity response measured for the meat extracts (TA98 revertants) was similar to the mutagenic activity calculated from the mass of heterocyclic amines present. The rate of formation of PhIP in a model system containing creatinine and phenylalanine heated in 80% diethylene glycol was compared with PhIP formation during meat frying. The apparent heats of activation were 6.5 kcal/mol in the model system compared with 6.0 kcal/mol in the fried meat patties. The increase in PhIP and MeIQx formation fitted an exponential function over the range 0 to 11 min and from 150 to 230 degrees C. This report shows clearly that increases in cooking temperature and time can have a profound effect on the amounts of heterocyclic amines generated and subsequently consumed in the diet.

  1. Improve the biodegradability of post-hydrothermal liquefaction wastewater with ozone: conversion of phenols and N-heterocyclic compounds.

    Yang, Libin; Si, Buchun; Martins, Marcio Arêdes; Watson, Jamison; Chu, Huaqiang; Zhang, Yuanhui; Tan, Xiaobo; Zhou, Xuefei; Zhang, Yalei

    2017-04-01

    Hydrothermal liquefaction is a promising technology to convert wet biomass into bio-oil. However, post-hydrothermal liquefaction wastewater (PHWW) is also produced during the process. This wastewater contains a high concentration of organic compounds, including phenols and N-heterocyclic compounds which are two main inhibitors for biological treatment. Thus, proper treatment is required. In this work, ozone was used to convert phenols and N-heterocyclic compounds with a dosage range of 0-4.64 mg O 3 /mL PHWW. After ozone treatment, the phenols were fully converted, and acids were produced. However, N-heterocyclic compounds were found to have a low conversion rate (21.7%). The kinetic analysis for the degradation of phenols and N-heterocyclic compounds showed that the substitute played an important role in determining the priority of ozone reactions. The OH moiety in the ring compounds (phenols and pyridinol) may form hydroxyl radical, which lead to an efficient reaction. A substantial improved biodegradability of PHWW was observed after ozone treatment. The ratio of BOD 5 /COD was increased by about 32.36%, and reached a maximum of 0.41. The improved biodegradability of PHWW was justified by the conversion of phenols and N-heterocyclic compounds.

  2. Extended mechanistic aspects on photoinitiated polymerization of 1,6-hexanediol diacrylate by hexaarylbisimidazoles and heterocyclic mercapto compounds.

    Berdzinski, Stefan; Strehmel, Nadine; Lindauer, Heike; Strehmel, Veronika; Strehmel, Bernd

    2014-05-01

    Chlorine substituted hexaarylbisimidazole (o-Cl-HABI) efficiently initiates radical polymerization of multifunctional acrylic esters in the presence of a heterocyclic mercapto compound if the latter can form its tautomeric thione. Exposure of o-Cl-HABI results in lophyl radicals, which efficiently add to the thione in the first step while the second step releases a highly reactive thiyl radical from this intermediate. LC-MS and CID-MS measurements support this reaction scheme. Furthermore, photo-DSC experiments applying UV light between 320 and 380 nm showed that mercaptotriazole and phenylmercaptotriazole exhibited the best reactivity in the monomer 1,6-hexanediol diacrylate (HDDA) while alkyl substituted mercaptotriazoles showed less reactivity. Change of the triazole heterocycle by mercaptoimidazole resulted in a significant decrease of photoinitiation efficiency. This heterocycle does not form the corresponding thione in HDDA as shown by NMR measurements. Replacement of mercaptotriazole by an alkylthiol leads to a system showing the lowest photoinitiation efficiency in this series. Formation of thione structure in the case of heterocyclic mercapto compounds may cause higher reactivity of the heterocyclic mercapto compounds with the lophyl radical in the monomer chosen.

  3. Heterocyclic Anticancer Compounds: Recent Advances and the Paradigm Shift towards the Use of Nanomedicine’s Tool Box

    Pedro Martins

    2015-09-01

    Full Text Available The majority of heterocycle compounds and typically common heterocycle fragments present in most pharmaceuticals currently marketed, alongside with their intrinsic versatility and unique physicochemical properties, have poised them as true cornerstones of medicinal chemistry. Apart from the already marketed drugs, there are many other being investigated for their promising activity against several malignancies. In particular, anticancer research has been capitalizing on the intrinsic versatility and dynamic core scaffold of these compounds. Nevertheless, as for any other promising anticancer drugs, heterocyclic compounds do not come without shortcomings. In this review, we provide for a concise overview of heterocyclic active compounds and families and their main applications in medicine. We shall focus on those suitable for cancer therapy while simultaneously addressing main biochemical modes of action, biological targets, structure-activity relationships as well as intrinsic limitation issues in the use of these compounds. Finally, considering the advent of nanotechnology for effective selective targeting of drugs, we shall discuss fundamental aspects and considerations on nanovectorization of such compounds that may improve pharmacokinetic/pharmacodynamic properties of heterocycles.

  4. Identification of sulfur heterocycles in coal liquids and shale oils. Technical progress report, August 1, 1980-May 1, 1981

    Lee, M. L.; Castle, R. N.

    1981-01-01

    The sulfur heterocycle separation scheme which was described in the last progress report was evaluated for quantitative recovery of individual components. The results indicate that recoveries can range from 10% to approx. 30% depending on the structure of the compound. During this period, 23 unsubstituted sulfur-containing heterocyclic ring systems were synthesized in oder to confirm GC/MS identifications and for biological testing. The four possible 3-ring heterocycles and the thirteen possible 4-ring heterocycles were tested for mutagenic activity in the histidine reversion (Ames assay) system. One of the 3-ring isomers, naphtho(1,2-b)-thiophene, and six of the 4-ring isomers induced mutations in Salmonella test strains. One of these compounds, phenanthro(3,4-b)thiophene, displayed approximately the same mutagenic activity as benzo(a)pyrene. A two-step adsorption chromatographic procedure was developed in order to fractionate synthetic fuels into various chemical-type classes for studying the relative concentrations and mutagenic activities of the various types. An SRC-II Heavy Distillate was fractionated into aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, sulfur heterocycles, indoles and carbazoles, azaarenes, and amino polycyclic aromatic hydrocarbons. It was found that the amino-PAH fraction contained most of the mutagenic activity. A survey was made for compounds containing both nitrogen and sulfur heteroatoms in their structures. A number of these compounds were detected by GC using nitrogen- and sulfur-selective detection.

  5. N,S,O-Heterocycles in Aged Champagne Reserve Wines and Correlation with Free Amino Acid Concentrations.

    Le Menn, Nicolas; Marchand, Stephanie; de Revel, Gilles; Demarville, Dominique; Laborde, Delphine; Marchal, Richard

    2017-03-22

    Champagne regulations allow winegrowers to stock still wines to compensate for quality shifts in vintages, mainly due to climate variations. According to their technical requirements and house style, Champagne producers use these stored wines in their blends to enhance complexity. The presence of lees and aging at low pH (2.95-3.15), as in Champagne wines, lead to several modifications in wine composition. These conditions, combined with extended aging, result in the required environment for the Maillard chemical reaction, involving aromatic molecules, including sulfur, oxygen, and nitrogen heterocycles (such as thiazole, furan, and pyrazine derivatives), which may have a sensory impact on wine. Some aromatic heterocycles in 50 monovarietal wines aged from 1 to 27 years provided by Veuve Clicquot Ponsardin Champagne house were determined by the SPME-GC-MS method. The most interesting result highlighted a strong correlation between certain heterocycle concentrations and wine age. The second revealed a correlation between heterocyclic compound and free amino acid concentrations measured in the wines, suggesting that these compounds are potential aromatic precursors when wine is aged on lees and, thus, potential key compounds in the bouquet of aged Champagnes. The principal outcome of these assays was to reveal, for the first time, that aromatic heterocycle concentrations in Champagne base wines are correlated with wine age.

  6. SUR. Breve informe de la Expedición Yelcho al Polo Sur (1909-1910

    Ursula K. Le Guin

    2013-12-01

    Full Text Available Ursula K. Le Guin Escritora norteamericana, famosa por sus obras de ciencia fi cción y fantasía, en las cuales el tema de género ocupa una posición central. Ganadora de los premios Hugo y Nébula que la catapultaron a la fama. “SUR. A summary report of the Yelcho expedition to the Antarctic, 1909-1910”. Apáreció publicado por primera vez en la revista New Yorker, el 1° de febrero de 1982. La palabra SUR aparece en español en el original. (http://www.newyorker.com/ar Traducción de Susana E. Matallana Peláez

  7. Sexualidad, migraciones y fronteras en contextos de integración sur-sur

    Martha Cecilia Ruiz

    Full Text Available Resumen Este artículo se pregunta sobre los procesos de diferenciación, jerarquización e inclusión/exclusión de poblaciones migrantes en contextos migratorios sur-sur, y sobre el rol que juega la sexualidad en estos procesos. Partiendo de un estudio etnográfico sobre las migrantes peruanas y colombianas en el sector del comercio sexual de Ecuador, se analiza la manera en que la sexualidad se convierte en un sitio privilegiado para re-imaginar las diferencias y jerarquías nacionales en un mundo globalizado e integrado regionalmente, y se explica cómo los regímenes de control sobre las migraciones y la sexualidad femenina se articulan entre sí para restablecer el orden idealizado de la nación.

  8. Amides with nitrogenous heterocyclic substituent, their manufacturing process and their use to draw out selectively Actinium series (III) and to separate them in particular from Lanthanides (III)

    Cuillerdier, C.; Musikas, C.

    1993-01-01

    Present invention is concerned with new amides with nitrogenous heterocyclic substituent utilizable to separate trivalent actinium series from trivalent lanthanides. In these molecules, it is possible to obtain particularly covalent liaison which has more affinity with 5f series, that is to say actinium series; included a manufacturing process for these amides with nitrogenous heterocyclic substituent

  9. Elution behavior of N-heterocyclic derivatives of mixed ruthenium(II)-sulfoxide complexes in reversed-phase high-performance liquid chromatography

    Toma, H.E.; Silva, D.O.

    1991-01-01

    The elution behaviour of a series of dichlorobis-(dimethylsulfoxide)bis(N-heterocyclic) ruthenium(II) complexes has been investigated using reversed-phase HPLC. Similar trends as those displayed by the free N-heterocyclic bases have been observed for the complexes, essentially reflecting the hydrophobic properties of the aromatic ligands. (orig.)

  10. Synthesis, characterization and applications of some novel mordent and heterocyclic disperse dyes on polyester and wool fibers

    Hitendra Mangubhai Patel

    2012-10-01

    Full Text Available The novel mordent and disperse heterocyclic dyes were prepared by coupling of various diazo solution of aromatic amines with 1-[(2-butyl-2,3-dihydrobenzofuran-3-yl]-1-(4-hydroxyphenylmethanone. The resultant mordent and disperse heterocyclic dyes were characterized by elemental analyses, IR and 1H-NMR and 13C-NMR spectral studies. The UV-visible spectral data have also been discussed in terms of structural property relationship. The dyeing assessment of all the mordent and disperse heterocyclic dyes was evaluated on wool and polyester textile fibers. The results of antibacterial studies of chrome pretreated fabrics revealed that the toxicity of mordented dyes against Escherichia coli, Staphylococcus aureus, Salmonella typhi, Bacillus subtilis bacteria was fairly good.

  11. Synthesis, characterization and dyeing behavior of heterocyclic acid dyes and mordent acid dyes on wool and silk fabrics

    Patel Hitendra M.

    2012-01-01

    Full Text Available Novel heterocyclic acid and mordent acid dyes were synthesized by the coupling of diazonium salt solution of different aromatic amines with 2- butyl-3-(4-hydroxybenzoylbenzofuran. The resulting heterocyclic acid dyes were characterized by spectral techniques, i.e., elemental analysis, IR, 1HNMR, 13C-NMR spectral studies and UV- visible spectroscopy. The dyeing performance of all the heterocyclic acid dyes was evaluated on wool and silk fabrics. The dyeing of chrome pre treated wool and silk fabrics showed better hues on mordented fabrics. Dyeing of wool and silk fabrics resulted in pinkish blue to red shades with very good depth and levelness. The dyed fabrics showed excellent to very good light, washing, perspiration, sublimation and rubbing fastness.

  12. Prediction model of biocrude yield and nitrogen heterocyclic compounds analysis by hydrothermal liquefaction of microalgae with model compounds.

    Sheng, Lili; Wang, Xin; Yang, Xiaoyi

    2018-01-01

    The model of biocrude yield and the nitrogen heterocyclic compounds in biocrude of microalgae hydrothermal liquefaction are two of the most concerned issues in this field at present. This study explored a hydrothermal liquefaction biocrude yield model involved in the interaction among biochemical compounds in microalgae and analysed nitrogen heterocyclic compounds in biocrude. The model compound (castor oil, soya protein and glucose) and Nanochloropsis were liquefied at 280°C for 1h. The products were analyzed by GC-MS, element analysis and FTIR. The results suggested that interactions among different components in microalgae enhanced biocrude yield. The biocrude yield prediction model involved cross-interactions performed more accurate than previous models.When the ratio of protein and carbohydrate around 3, the cross-interaction and nitrogen heterocyclic compounds in biocrude would both reach the highest extent. Copyright © 2017. Published by Elsevier Ltd.

  13. Mixed-ligand complexes of copper (II with ditiolfenols and heterocyclic diamines

    K. A. Kuliev

    2017-01-01

    Full Text Available By the methods spectrophotometric methods was investigated complex formation of copper with 2,6-ditiolphenol and its derivatives (2,6-ditiol-4-methylphenol, 2,6-ditiol-4-ethylphenol and 2,6-ditiol-4-tert-buthylphenol in the presence of heterocyclic diamines. As heterocyclic diamines phenantroline (Fen, batophenantroline and dipyridile were used. It was established, that mixedligand complex were formed in weak acidic medium (pHop=6,0-8,5. Maximum of light absorption observed at (=522–550 nm. Molar coefficient of light absorption was ( = (3.08–4.92?104. The stoichiometry of complexes had been discovered using shift the equilibrium and relative yield methods. During the extraction of copper(II complexes with ditiol-phenols with the presence of heterocyclic diamines there was discovered that there is no chlorophorm molecules in the composition of the extracted complexes. IR spectra shows that hydroxyl group is involved to the formation of a bond with the metal and that phenantroline is included in the composition of the copper complex. In the organic phase mixed-ligand complexes have the monomeric form and can’t polymerize; that fact can be proved by calculations. By dint of spectrophotometric, IR-spectroscopic, thermogravimetric experiments and some published data we were able to determine the structural formula of complexes. Also had been determined main spectrophotometric characteristics of copper(II mixed-ligand complexes: pH of the beginning of the deposition, optimal pH, detection limit and sensivity. For separation and finding copper, we studied the effect of interfering foreign ions: alkali, alkaline earth and rare earth elements, as well as acid anions selected masking reagents. On the base of the results was offered photometric method for determination of copper in steel different trade-marks and in food. This method characterized by good reproduction (relatively standard deviation no more 0.05 and low limit of discovery.

  14. A Photolabile Linker for the Solid-Phase Synthesis of Peptide Hydrazides and Heterocycles

    Qvortrup, Katrine; Komnatnyy, Vitaly V.; Nielsen, Thomas Eiland

    2014-01-01

    A photolabile hydrazine linker for the solid-phase synthesis of peptide hydrazides and hydrazine-derived heterocycles is presented. The developed protocols enable the efficient synthesis of structurally diverse peptide hydrazides derived from the standard amino adds, including those with side......-chain protected residues at the C-terminal of the resulting peptide hydrazide, and are useful for the synthesis of dihydropyrano[2,3-c]pyrazoles. The linker is compatible with most commonly used coupling reagents and protecting groups for solid-phase peptide synthesis....

  15. A molecular dynamics study of lithium-containing aprotic heterocyclic ionic liquid electrolytes

    Lourenço, Tuanan C.; Zhang, Yong; Costa, Luciano T.; Maginn, Edward J.

    2018-05-01

    Classical molecular dynamics simulations were performed on twelve different ionic liquids containing aprotic heterocyclic anions doped with Li+. These ionic liquids have been shown to be promising electrolytes for lithium ion batteries. Self-diffusivities, lithium transference numbers, densities, and free volumes were computed as a function of lithium concentration. The dynamics and free volume decreased with increasing lithium concentration, and the trends were rationalized by examining the changes to the liquid structure. Of those examined in the present work, it was found that (methyloxymethyl)triethylphosphonium triazolide ionic liquids have the overall best performance.

  16. Cascade olefin isomerization/intramolecular Diels-Alder reaction catalyzed by N-heterocyclic carbenes.

    Kowalczyk, Marcin; Lupton, David W

    2014-05-19

    The addition of an N-heterocyclic carbene to the carbonyl group of an α,β,γ,δ-unsaturated enol ester affords a hemiacetal azolium intermediate that enables a cascade olefin isomerization/Diels-Alder reaction, for which mechanistic studies implicate Lewis base catalysis. Preliminary studies into the utility of the products have been undertaken with reductive and oxidative cleavage, giving materials for potential use in complex-target synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Domino approach to 2-aroyltrimethoxyindoles as novel heterocyclic combretastatin A4 analogues.

    Arthuis, Martin; Pontikis, Renée; Chabot, Guy G; Quentin, Lionel; Scherman, Daniel; Florent, Jean-Claude

    2011-01-01

    Two series of 2-aroyltrimethoxyindoles were designed to investigate the effects of the replacement of the trimethoxyphenyl ring of phenstatin with a trimethoxyindole moiety. These compounds were efficiently prepared through a domino palladium-catalyzed sequence from 2-gem-dibromovinylanilines substituted by three methoxy groups and arylboronic acids under carbon monoxide atmosphere. These novel heterocyclic combretastatin A4 analogues were evaluated for their cell growth inhibitory properties and their ability to inhibit the tubulin polymerization. Copyright © 2010 Elsevier Masson SAS. All rights reserved.

  18. Synthesis and biological evaluation of novel heterocyclic derivatives of combretastatin A-4.

    Nguyen, Thi Thanh Binh; Lomberget, Thierry; Tran, Ngoc Chau; Colomb, Evelyne; Nachtergaele, Lore; Thoret, Sylviane; Dubois, Joëlle; Guillaume, Joren; Abdayem, Rawad; Haftek, Marek; Barret, Roland

    2012-12-01

    A novel series of combretastatin A-4 heterocyclic analogues was prepared by replacement of the B ring with indole, benzofurane or benzothiophene, attached at the C2 position. These compounds were evaluated for their abilities to inhibit tubulin assembly: derivative cis3b, having a benzothiophene, showed an activity similar to those of colchicine or deoxypodophyllotoxine. The antiproliferative and antimitotic properties of cis3b against keratinocyte cancer cell lines were also evaluated and the intracellular organization of microtubules in the cells after treatment with both stereoisomers of 3b was also determined, using confocal microscopy. Copyright © 2012 Elsevier Ltd. All rights reserved.

  19. An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles

    Marcus Baumann

    2013-10-01

    Full Text Available This review which is the second in this series summarises the most common synthetic routes as applied to the preparation of many modern pharmaceutical compounds categorised as containing a six-membered heterocyclic ring. The reported examples are based on the top retailing drug molecules combining synthetic information from both scientific journals and the wider patent literature. It is hoped that this compilation, in combination with the previously published review on five-membered rings, will form a comprehensive foundation and reference source for individuals interested in medicinal, synthetic and preparative chemistry.

  20. Highly selective deuteration of pharmaceutically relevant nitrogen-containing heterocycles: a flow chemistry approach.

    Ötvös, Sándor B; Mándity, István M; Fülöp, Ferenc

    2011-08-01

    A simple and efficient flow-based technique is reported for the catalytic deuteration of several model nitrogen-containing heterocyclic compounds which are important building blocks of pharmacologically active materials. A continuous flow reactor was used in combination with on-demand pressure-controlled electrolytic D(2) production. The D(2) source was D(2)O, the consumption of which was very low. The experimental set-up allows the fine-tuning of pressure, temperature, and flow rate so as to determine the optimal conditions for the deuteration reactions. The described procedure lacks most of the drawbacks of the conventional batch deuteration techniques, and additionally is highly selective and reproducible.

  1. Unexpected rearrangements in the synthesis of an unsymmetrical tridentate dianionic N-heterocyclic carbene

    Despagnet-Ayoub, Emmanuelle; Miqueu, Karinne; Sotiropoulos, Jean-Marc; Henling, Lawrence M.; Day, Michael W.; Labinger, Jay A.; Bercaw, John E.

    2013-01-01

    Starting from the same ethylenediamine species, three valuable carbene precursors were synthesized under differing conditions: a tridentate dianionic N-heterocyclic carbene bearing an aniline, a phenol and a central dihydroimidazolium salt, its benzimidazolium isomer by intramolecular rearrangement and a dicationic benzimidazolium-benzoxazolium salt by changing the Brønsted acid from HCl to HBF4. A DFT study was performed to understand the rearrangement pathway. The structure of a bis[(NCO)carbene] zirconium complex was determined. © 2013 The Royal Society of Chemistry.

  2. Enantioselective N-Heterocyclic Carbene Catalysis via the Dienyl Acyl Azolium.

    Gillard, Rachel M; Fernando, Jared E M; Lupton, David W

    2018-04-16

    Herein we report the enantioselective N-heterocyclic carbene catalyzed (4+2) annulation of the dienyl acyl azolium with enolates. The reaction exploits readily accessible acyl fluorides and TMS enol ethers to give a range of highly enantio- and diastereo-enriched cyclohexenes (most >97:3 er and >20:1 dr). The reaction was found to require high nucleophilicity NHC catalysts with mechanistic studies supporting a stepwise 1,6-addition/β-lactonization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Reactions of secondary propargylamines with heteroallenes for the synthesis of diverse heterocycles

    Peshkov, Vsevolod A.; Pereshivko, Olga P.; Nechaev, Anton A.; Peshkov, Anatoly A.; Van der Eycken, Erik V.

    2018-01-01

    This focused review aims to summarize recent developments in the processes involving additions of secondary propargylamines to various heteroallenes and subsequent transition metal-catalyzed or electrophile-mediated cyclizations. The utility of this convenient and tunable strategy spans from the carbon dioxide fixation and target-oriented synthesis of complex natural and biologically active products to the generation of extended synthetic libraries of diverse oxygen-, nitrogen- and sulfur-containing heterocycles. For comparative purposes, the analogous transformations of propargylic alcohols are also highlighted in this account.

  4. Solid-supported synthesis: From pharmacologically relevant heterocycles to biologically active surfaces

    Komnatnyy, Vitaly V.

    for solid-phase synthesis, methods for on - and off-bead screening of combinatorial libraries and their applic ation to various biological targets. The first part of the thesis is dedicated to the development of methodology for the synthesis of structurally diverse heterocyclic scaffolds via N...... methods for the controlled organo-functionalization of titanium, one of the most prominent materials in medicinal device industry, have been suggested . Initial acidic and oxidative treatment s of the metal surface genera te reactive hydroxyl moieties , which are subsequently modified with synthetically...... versatile amine -containing reagents. Subsequent applications in antimicrobial peptide synthesis, metal -catalysis, release from the surface, and polymer grafti ng, are also presented....

  5. Synthesis of heterocycles: Indolo (2,1-a) isoquinolines, renewables, and aptamer ligands for cellular imaging

    Beasley, Jonathan [Ames Laboratory (AMES), Ames, IA (United States)

    2013-01-01

    In this thesis, we explore both total syntheses and methodologies of several aromatic heterocyclic molecules. Extensions of the Kraus indole synthesis toward 2-substituted and 2,3-disubstituted indoles, as well as biologically attractive indolo[2,1-a]isoquinolines are described. Recent renewable efforts directed to commodity maleic acid and the first reported furan-based ionic liquids are described. Our total synthesis of mRNA aptamer ligand PDC-Gly, and its dye coupled forms, plus aminoglycoside dye coupled ligands used in molecular imaging, are described.

  6. Latent ruthenium–indenylidene catalysts bearing a N-heterocyclic carbene and a bidentate picolinate ligand

    Thibault E. Schmid

    2015-09-01

    Full Text Available A silver-free methodology was developed for the synthesis of unprecedented N-heterocyclic carbene ruthenium indenylidene complexes bearing a bidentate picolinate ligand. The highly stable (SIPr(picolinateRuCl(indenylidene complex 4a (SIPr = 1,3-bis(2-6-diisopropylphenylimidazolidin-2-ylidene demonstrated excellent latent behaviour in ring closing metathesis (RCM reaction and could be activated in the presence of a Brønsted acid. The versatility of the catalyst 4a was subsequently demonstrated in RCM, cross-metathesis (CM and enyne metathesis reactions.

  7. Improving cytotoxic properties of ferrocenes by incorporation of saturated N-heterocycles

    Hodík, Tomáš; Lamač, Martin; Červenková Šťastná, Lucie; Cuřínová, Petra; Karban, Jindřich; Skoupilová, H.; Hrstka, R.; Císařová, I.; Gyepes, Robert; Pinkas, Jiří

    2017-01-01

    Roč. 846, OCT 2017 (2017), s. 141-151 ISSN 0022-328X R&D Projects: GA ČR(CZ) GAP207/12/2368; GA ČR(CZ) GA17-05838S Institutional support: RVO:61388955 ; RVO:67985858 Keywords : metallodrugs * ferrocene derrivatives * N-heterocycles Subject RIV: CF - Physical ; Theoretical Chemistry; CF - Physical ; Theoretical Chemistry (UCHP-M) OBOR OECD: Inorganic and nuclear chemistry; Physical chemistry (UCHP-M) Impact factor: 2.184, year: 2016

  8. Synthesis and Antibacterial Evaluation of Novel Heterocyclic Compounds Containing a Sulfonamido Moiety

    Eman A. El-Bordany

    2013-01-01

    Full Text Available Aiming for the synthesis of new heterocyclic compounds containing a sulfonamido moiety suitable for use as antibacterial agents, the precursor ethyl {[4-N-(4,6-dimethylpyrimidin-2-ylsulfamoyl]phenylazo}cyanoacetate was reacted with a variety of active methylene compounds producing pyran, pyridine and pyridazine derivatives. Also, the reactivity of the precursor hydrazone towards hydrazine derivatives to give pyrazole and oxazole derivatives was studied. On the other hand, treatment of the same precursor with urea, thiourea and/or guanidine hydrochloride furnished pyrimidine and thiazine derivatives, respectively. The newly synthesized compounds were tested for antibacterial activity, whereby eight compounds were found to have high activities.

  9. Chromatographic methods for determination of metals as chelate compounds with heterocyclic azo reagents

    Basova, E.M.; Bol'shova, T.A.; Shpigun, O.A.; Ivanov, V.M.

    1993-01-01

    Methods for separation and concentration of transition metals as well as cadmium in form of chelates with heterocyclic azo compounds namely, PAN(1-(2-pyridylaso)-2-naphthol), PAR(4-(2-pyridylazo)-resorcin), Br-PAAP (2-(5-bromine-2-pyridylazo)-5-diethyl aminophenol) are considered. The Br-PAAP reagent is the most sensitive and widely-applied one in extraction and highly-efficient liquid chromatography. Methods of sorption concentration with subsequent element determination directly on the sorbent without microelements separation or destruction are the most promissing ones

  10. Half -sand wish ruthenium complexes of heterocyclic-dithio carboxylato ligands

    El-khateeb, M.; Al-Noaimi, M.; Harb, M.; Gorls, H.; Weigand, W.

    2008-01-01

    The heterocyclic-dithio carboxylato complexes Cp Ru(PPh 3 )(κ 2 S,S-S 2 C-h et) [h et= 2-C 4 H 3 O (1), 2-C 4 H 3 S (2), 1-C 4 H 8 N (3)] are obtained by the reaction of the ruthenium chloride, Cp Ru(PPh 3 ) 2 CI, with the anions, h et-CS 2 . The X-ray structure of Cp Ru(PPh 3 )(κ 2 S, S-S 2 C-1- C 4 H 8 N) (3) is determined by single crystal X-ray diffraction.

  11. Sorption of europium (3) by polymer sorbents with grafted heterocyclic nitrogen-containing groupings

    Bel'tyukova, S.V.; Kravchenko, T.B.; Balamtsarashvili, G.M.; Roska, A.S.

    1990-01-01

    On polymer sorbents (copolymer of styrene-divinylbenzene) with grafted heterocyclic nitrogen-containing functional groupings of tetrazole, triazole and imidazole (sorbents 1,2,3, respectively). It is stated that europium sorption takes place from neutral solutions in presence of organic solvents. Luminescent properties of europium on sorbent are used to develope methods of its determination in high purity lanthanide and yttrium oxides. Europium determination limits consist 7.5·10 -5 μg/ml on 1 and 3 sorbents and 1.5·10 -4 μg/ml on sorbent 2, S p value is 0.089 and 0.075, respectivaly

  12. Physicochemical study of niobium(5) complexes with rhodanide and heterocyclic bases

    Lobanov, F.I.; Zatonskaya, V.M.; Gibalo, I.M.

    1980-01-01

    Mixed complexes of niobium rhodanide with organic heterocyclic bases-1,10-phenanthroline; 2,3-dimethyl-1,10-phenanthroline; 4,7-diphenyl-1,10 phenanthroline-bathophenanthroline; S-collidine are singled out. The composition of the compounds is established. The character of the bonds Nb-O, Nb-NCS, Nb-basis is studied using the method of IR spectroscopy. Derivatogravimetric analysis of the complexes singled out has shown the complex character of their decomposition. The measurement of electric conductivity of the mixed complexes in dimethylformamide solutions has shown that they are binary electrolytes

  13. Simple Method of Preparation and Characterization of New Antifungal Active Biginelli Type Heterocyclic Compounds

    Velan, A. Senthilkumara; Joseph, J.; Raman, N.

    2008-01-01

    A simple, efficient and cost effective method is described for the synthesis of Biginelli type heterocyclic compounds of dihydropyrimidinones analogous. They were prepared from a reaction mixture consisting of substituted benzaldehydes, thiourea and ethylacetoacetate using ammonium dihydrogenphosphate as catalyst. The procedure for the preparation of the compounds is environmentally benign and safe which is advantageous in terms of experimentation, catalyst reusability, yields of the products, shorter reaction times and preclusion of toxic solvents. The four new synthesised compounds were tested for their antifungal activity. They have good antifungal activity comparing to the standard (Fluconazole). PMID:23997611

  14. Crystal and molecular structure of three molybdenum (6) dioxocomplexes with heterocyclic hydrazones

    Ilyukhin, A.B.; Sergienko, V.S.

    1994-01-01

    The X-ray diffraction investigation into three Mo(6) dioxocomplexes with heterocyclic hydrazones has been made. In all compounds the Mo atom has a deformed octahedral coordination by two O atoms of cis-dioxogroups, N atoms (azomethane), N (heterocyclie), O (phenol) of tridentate organic ligand. Sixth position in Mo coordination octahedron is due to O atom of methanol solvated molecule in the 1,3 structures or N atom of γ-picoline molecule in the 2 structure. The packing of structural units in the crystals of the 1-3 compounds is under consideration. 12 refs., 5 figs., 3 tabs

  15. Spectroscopic and electrochemical correlations in triangular ruthenium clusters containing N-heterocyclic ligands

    Cunha, C.J. da.

    1989-01-01

    A series of clusters of general formula [Ru sub(3) O (OOCCH sub(3)) sub(6) L sub(3)] sup(+), where L = N-heterocyclic ligands, were synthesized and characterized based on elemental analysis. UV-VIS and IR spectra. Voltametric studies revealed the existence of up to six acessible oxidation states, with a high degree of electronic delocalization. The Ru sub(3) O trigonal center possesses many delocalized electrons and can be visualized as a source of electrons. The ligands coordinated to the clusters tune their redox potentials, determine the differences in their electronic spectra, and are responsible for the special conditions required for their synthesis. (author)

  16. Bis-ligated Ti and Zr complexes of chelating N-heterocyclic carbenes

    El-Batta, Amer

    2011-07-01

    In this communication we report the synthesis of novel titanium and zirconium complexes ligated by bidentate "salicylaldimine-like" N-heterocyclic carbenes (NHC). Double addition of the NHC chelate to either TiCl4(thf)2 or ZrCl4 forms bis-ligated organometallic fragments with a distorted octahedral geometry. These complexes are rare examples of group IV transition-metal NHC adducts. Preliminary catalytic tests demonstrate that in the presence of methylaluminoxane (MAO) these complexes are useful initiators for the polymerization of ethylene and the copolymerization of ethylene with norbornene and 1-octene. © 2011 Elsevier B.V. All rights reserved.

  17. Heterocyclic amines content of meat and fish cooked by Brazilian methods

    Iwasaki, Motoki; Kataoka, Hiroyuki; Ishihara, Junko; Takachi, Ribeka; Hamada, Gerson Shigeaki; Sharma, Sangita; Le Marchand, Loïc; Tsugane, Shoichiro

    2010-01-01

    Heterocyclic amine (HCA) concentrations were measured in meat and fish samples cooked by pan-frying, grilling and churrasco (Brazilian barbecue) to various levels of doneness in accordance with the cooking methods most commonly used in Brazil. HCAs were extracted by the Blue-rayon absorption method and measured by liquid chromatography–mass spectrometry. 2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), and 2-amino-3,4,8-trimethylim...

  18. Reactions of secondary propargylamines with heteroallenes for the synthesis of diverse heterocycles

    Peshkov, Vsevolod A.

    2018-03-16

    This focused review aims to summarize recent developments in the processes involving additions of secondary propargylamines to various heteroallenes and subsequent transition metal-catalyzed or electrophile-mediated cyclizations. The utility of this convenient and tunable strategy spans from the carbon dioxide fixation and target-oriented synthesis of complex natural and biologically active products to the generation of extended synthetic libraries of diverse oxygen-, nitrogen- and sulfur-containing heterocycles. For comparative purposes, the analogous transformations of propargylic alcohols are also highlighted in this account.

  19. Effects of Electron Acceptors, Reducing Agents, and Toxic Metabolites on Anaerobic Degradation of Heterocyclic Compounds

    Licht, Dorthe; Ahring, Birgitte Kiær; Arvin, Erik

    1996-01-01

    Degradation of four heterocyclic compounds was examined under nitrate-reducing, sulphate-reducing and methanogenic conditions. Soil samples from a creosote-polluted site in Denmark were used as inoculum. Indole and quinoline were degraded under all redox conditions with the highest degradation...... of quinoline under sulphate-reducing conditions which was inhibited by sulphide at concentrations above 0.8 mM. Degradation of quinoline under methanogenic conditions was also inhibited by 3.2 mM sulphide used as a reducing agent, but sulphide had no inhibitory effect on the degradation of indole...... in methanogenic and sulphate-reducing soil slurries...

  20. RESEARCH REGARDING THE POTENTIAL ACTIVITY OF SOME HETEROCYCLIC COMPOUNDS ON PLANTS GROWTH AND DEVELOPMENT

    OANA-IRINA PATRICIU

    2017-06-01

    Full Text Available It is well known that growth and morphogenesis of plant tissue cultures can be improved by small amounts of some organic compounds. Heterocyclic compounds such as chromanones and thiazoles derivatives, valuable because of their potential biological activities, have also been reported as pesticides, herbicides and plant-growth regulators. In the present study, different concentrations of chromanones and thiazoles derivatives were employed to evaluate their effects on plantlets growth of Ocimum basilicum L. and Echinacea purpurea L. The studied compounds were proved to be growth inhibitors at high concentrations. A growth stimulation effect was registered at low concentration.

  1. Pulse gas chromatographic study of adsorption of substituted aromatics and heterocyclic molecules on MIL-47 at zero coverage.

    Duerinck, Tim; Couck, Sarah; Vermoortele, Frederik; De Vos, Dirk E; Baron, Gino V; Denayer, Joeri F M

    2012-10-02

    The low coverage adsorptive properties of the MIL-47 metal organic framework toward aromatic and heterocyclic molecules are reported in this paper. The effect of molecular functionality and size on Henry adsorption constants and adsorption enthalpies of alkyl and heteroatom functionalized benzene derivates and heterocyclic molecules was studied using pulse gas chromatography. By means of statistical analysis, experimental data was analyzed and modeled using principal component analysis and partial least-squares regression. Structure-property relationships were established, revealing and confirming several trends. Among the molecular properties governing the adsorption process, vapor pressure, mean polarizability, and dipole moment play a determining role.

  2. Cationic bis-N-heterocyclic carbene (NHC) ruthenium complex: Structure and application as latent catalyst in olefin metathesis

    Rouen, Mathieu

    2014-09-11

    An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions.

  3. Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

    Sharanin, Yu A; Goncharenko, M P; Litvinov, Victor P

    1998-01-01

    Published data on the methods for synthesis of carbo- and heterocyclic compounds based on reactions of α,β-unsaturated nitriles with carbonyl compounds and activated phenols are surveyed. It is demonstrated that all these reactions occur via nucleophilic addition of the carbanion generated from a carbonyl compound to the double bond of an unsaturated nitrile (the Michael reaction). The main routes of transformation of the adducts into carbo- and heterocyclic compounds are considered. The methods for regioselective preparation of fused 4H-pyrans or 1,4-dihydropyridines by varying conditions of cyclisation of Michael adducts are discussed. The bibliography includes 249 references.

  4. Quantum-chemical investigation of the 1,2-proton shift in protonated five-membered aromatic heterocycles

    Abronin, I.A.; Gorb, L.G.; Litvinov, V.P.

    1985-01-01

    Calculations of the energetics of the 1,2-proton shift in protonated five-membered aromatic heterocycles - pyrrole, furan, and thiophene - have been carried out by the SCF MO LCAO method in the MINDO/3 approximation and nonempirically on the OST-3GF (OST-3GF) basis. The general features of this process, and also the influence of solvation and of taking into account the vacant d-AOs of the sulfur atom in the protonated form of thiophene on the results of the calculation are considered. The results obtained have been used for a discussion of the activity and selectivity of the heterocycles considered in aromatic electrophilic substitution reactions

  5. Solid-phase synthesis of compounds of europium and terbium with nitrogen-containing heterocyclic compounds under mechanical activation

    Kalinovskaya, I.V.; Karasev, V.E.

    2000-01-01

    Effect of solvents and parameters of mechanical treatment on basic regularities of synthesis of rare earth compounds with nitrogen-containing heterocyclic compounds is studied. It is shown that interaction on europium (3) and terbium (3) nitrates with nitrogen-containing heterocyclic compounds leads to formation of compounds of Ln(NO 3 )·2D composition, where Ln=Eu, Tb; D=2,2-dipyridyl, 1,10-phenanthroline, diphenylguanidine. Effect of conditions of mechanical treatment and different additions on process and yield of products is studied. Compounds prepared are characterized by the methods of chemical element analysis, IR spectroscopy and luminescent spectroscopy [ru

  6. Impact du cordon sableux déposé à l’embouchure du site Ramsar de l’estuaire de l’Oued Massa (Maroc sur l’hydrologie et l’avifaune

    M. EL BEKKAY

    2014-03-01

    Full Text Available Situé sur un des principaux axes de migration des oiseaux d’eau entre l’Europe et l’Afrique, l’estuaire de l’oued Massa, inscrit dans la liste Ramsar depuis 2005, a connu des modifications hydrologiques importantes, à la suite de l’installation en amont du barrage Youssef Ben Tachfine en 1972. En effet, l’installation de ce barrage a induit le dépôt d’un cordon de sable au niveau de l’embouchure, séparant les eaux de l’oued de celles de l’océan atlantique et transformant le site d’un écosystème estuarien en écosystème lagunaire. Le site est aussi le siège de changements irréguliers, enregistrés lors de disparitions temporaires du cordon de sable survenues à la suite des lâchés de barrages lors des précipitations abondantes comme c’était le cas en 1983, 1992, 1996 et 2010. Ce travail de recherche vise à étudier l’effet des modifications de l’écosystème à la suite de la disparition du cordon du sable de l’embouchure, sur l’évolution des paramètres physicochimiques du milieu et sur les oiseaux fréquentent le site. Pour ce faire plusieurs paramètres physicochimiques de l’eau (pH, oxygène dissous, température, salinité, azote ammoniacal, ortho-phosphate et nitrates ont été mesurés avant (2009 et après (2010 la dernière disparition du cordon de sable survenue en février 2010. Concernant l’influence des changements de l’écosystème sur l’avifaune, elle a été évaluée grâce au suivi de 7 espèces d’oiseaux parmi les plus caractéristiques de ce site Ramsar. Les résultats obtenus montrent que le passage de l’embouchure d’un état lagunaire vers un état estuarien à la suite de la disparition du cordon sableux s’est traduit principalement par l’amélioration de la qualité des eaux par accroissement des valeurs de l’oxygène dissous. Le milieu a connu aussi une augmentation de la salinité. Concernant les oiseaux d’eau, les sept espèces étudiées ont

  7. Taxes sur les cigarettes en Tanzanie | CRDI - Centre de recherches ...

    On s'attend à ce que cette hausse du tabagisme ait d'importantes répercussions sur la santé publique et le développement économique. Il ressort de l'expérience d'autres régions que le moyen le plus efficace de renverser une telle tendance consiste à augmenter les taxes sur les cigarettes. Toutefois, les responsables des ...

  8. Le lancement canadien du Rapport sur les politiques alimentaires ...

    1 mai 2018 ... Cet événement sera filmé, puis accessible en ligne sur la chaîne YouTube du CRDI. Le Rapport sur les politiques alimentaires mondiales 2018 passe en revue les principaux faits nouveaux et événements en matière de politiques alimentaires survenus au cours de l'année. D'éminents chercheurs ...

  9. Une nouvelle ouverture sur le monde pour les femmes | CRDI ...

    'appellent ailleurs dans le dédale d'étals et d'allées serrés. En plus de son travail sur le marché, Jertrudes est également secrétaire de l'association des femmes qui vendent sur ce marché. Le groupe est un endroit où elles ...

  10. Gestion des agroecosystemes sur le mont agou en zone forestiere ...

    Dans le but d'une meilleure mise en valeur de l'espace, plusieurs espèces végétales sont cultivées en association essentiellement avec Persea americana. L'approche méthodologique est basée sur des inventaires floristiques et écologiques sur 45 placettes de 25 m x 25 m dans les agrosystèmes. Une diversité de 85 ...

  11. Recherche en partenariat sur la transition nutritionnelle et les ...

    l'évolution du risque a suivi et a débouché sur une stratégie de prévention ... de recherche ont pu avoir un impact sur les politiques et pro- .... Deux études étaient donc entreprises ..... à la même thématique et de recruter par eux-mêmes les.

  12. Des pratiques culturales influent sur les attaques de deux ravageurs ...

    La culture de tomate est attaquée par plusieurs ravageurs dont Helicoverpa armigera et Tuta absoluta. Dans le but d'évaluer l'effet des pratiques culturales de la tomate sur ces principaux ravageurs dans les Niayes (Sénégal), un échantillonnage de 98 parcelles est effectué, sur quatre cycles de culture en saison sèche, de ...

  13. Taxes sur les cigarettes en Tanzanie | IDRC - International ...

    Taxes sur les cigarettes en Tanzanie. De 2002 à 2007, le tabagisme a connu une hausse de 20 % en Tanzanie, une augmentation qui devrait atteindre 46 % en 2016 si la tendance se maintient. On s'attend à ce que cette hausse du tabagisme ait d'importantes répercussions sur la santé publique et le développement ...

  14. Analyse technico–économique des Aliments densifies sur les ...

    Une étude portant sur l'influence des aliments densifiés sur la performance de croissance des boucs roux de Maradi a été conduite entre juillet 2016 à septembre 2016. Quarante deux (42) boucs ont été répartis au hasard en six lots de sept individus. Chaque lot correspond à un aliment ou traitement préparé à partir des.

  15. Le Projet d’Ole Lando sur les Contrats

    Holle, Marie-Louise

    2017-01-01

    En 2016 le projet de recherche le plus important jusqu’à présent sur le droit nordique des contrats a pris fin et un livre, de presque 400 pages, en a marqué l’aboutissement. Le résultat du projet est un « restatement » tel qu’il existe aux États-Unis. Le Restatement porte sur les règles et les...

  16. Lignes directrices canadiennes sur la rhinosinusite chronique

    Kaplan, Alan

    2013-01-01

    Résumé Objectif Présenter un résumé clinique des lignes directrices canadiennes sur la rhinosinusite chronique (RSC) qui comporte des recommandations pertinentes aux médecins de famille. Qualité des données Les auteurs des lignes directrices ont effectué une recherche documentaire systématique dans la littérature médicale et ont rédigé une ébauche de recommandations. Une cote a été donnée à la fois en fonction de la fiabilité des données probantes et de la solidité des recommandations. On a sollicité les commentaires d’experts en contenu de l’extérieur, ainsi que l’aval des sociétés médicales (Association pour la microbiologie médicale et l’infectiologie Canada, Société canadienne d’allergie et d’immunologie clinique, Canadian Society of Otolaryngology—Head and Neck Surgery, Association canadienne des médecins d’urgence et Regroupement canadien des médecins de famille en santé respiratoire). Message principal Le diagnostic d’une RSC se fonde sur le type et la durée des symptômes et une constatation objective d’une inflammation de la muqueuse nasale ou des sinus paranasaux. La rhinosinusite chronique est catégorisée en fonction de la présence ou de l’absence de polypes nasaux et cette distinction entraîne des différences dans le traitement. On traite la rhinosinusite chronique avec polypes nasaux au moyen de corticostéroïdes par voie intranasale. Des antibiotiques sont recommandés quand les symptômes indiquent une infection (douleur ou purulence). Pour une RSC sans polypes nasaux, on recommande des corticostéroïdes par voie intranasale et des antibiotiques de deuxième ligne (par ex. combinaisons amoxicilline–acide clavulanique ou fluoroquinolones à activité accrue contre Gram positif). Une irrigation avec une solution saline, des stéroïdes par voie orale et des tests d’allergies pourraient être appropriées. Si le patient ne répond pas au traitement, il faudrait envisager d

  17. Quelques commentaires sur les personnages de fiction

    Umberto Eco

    2010-06-01

    Full Text Available L’auteur met en place des observations et développe des analyses sur le statut des personnages de fiction, mettant à contribution les ressources de l’histoire, de la littérature, de la sémiotique, de la logique et de la narratologie. De quelle vie particulière vivent les personnages de roman, qui fait que nous sommes capables de les tenir pour plus réels que des personnages réels, et que nous sommes enclins à éprouver les sentiments qu’ils éprouvent, même si nous savons qu’ils n’existent pas ? Comment ces personnages de fiction existent-ils, selon quelle « partition » leur existence se développe-t-elle au point d’interférer avec la nôtre ? L’interrogation porte sur la nature de ce flux émotionnel qui s’écoule du lecteur vers les personnages de fiction et les investit de valeur, sur ce qui se projette de la vie vers le roman, entraînant avec lui le lecteur qui se trouve de la sorte impliqué malgré lui dans l’histoire, et se trouve pris dans le mécanisme de l’identification et de la vie fictive.Some commentaries about fiction charactersPutting into form a number of observations and developing an analysis on the status of fiction characters, the author draws on resources coming from history, literature, semiotic, logic et narration. What is that particular life lived by fiction characters that enable us to consider them as being more real than real characters, and to experience the feelings that they experience, even though we know that they do not exist? How do these characters exist? In other words, according to what “script” does their existence develop to the point of interfering with ours? The questioning centres on the nature of the emotional flux which flows from the reader towards the fictional characters thus giving them value, and on what it is which is projected from real life towards the novel and which is capable of sweeping up the reader who, without having particularly intended to do

  18. Synthesis and Studies of Sulfur-Containing Heterocyclic Molecules for Molecular Electronics

    Mazzanti, Virginia

    This work describes the synthesis and studies of sulfur containing π conjugated heterocycles, which are considered interesting motifs in the field of molecular electronics. The first project, which is covered in Chapter 1, concerns the functionalization of tetracycle dibenzo[bc,fg][1,4]dithiapent......This work describes the synthesis and studies of sulfur containing π conjugated heterocycles, which are considered interesting motifs in the field of molecular electronics. The first project, which is covered in Chapter 1, concerns the functionalization of tetracycle dibenzo[bc,fg][1......,4]dithiapentalene (DDP). Attempts to prepare the S-O analog are also discussed. Chapter 2, focuses upon the studies performed on DDP and other sulfur containing π conjugated organic molecules. Organic Field Effect Transistor devices were fabricated and their performances were evaluated. Chapter 3 entails...... the synthesis of dimeric structures of redox active system tetrathiafulvalene (TTF). Molecules with different conjugation pathways bridging two TTFs were synthesized and studied using CV and DPV in order to probe the electronic interaction between these two redox units. The last aspect of this thesis, which...

  19. Preparation, one- and two-photon properties of carbazole derivatives containing nitrogen heterocyclic ring

    Zhang, Yichi; Wang, Ping; Li, Liang; Chen, Zhimin; He, Chunying; Wu, Yiqun

    Preparation of recording materials with high two-photon absorption activities is one of the important issues to superhigh- density two-photon absorption (TPA) three-dimensional (3D) optical data storage. In this paper, three new carbazole derivatives containing nitrogen heterocyclic ring with symmetric and asymmetric structures are prepared using ethylene as the π bridge between the carbazole unit and nitrogen heterocyclic ring, namely, 9-butyl-3-(2-(1,8- naphthyridin)vinyl)-carbazole (material 1), 9-butyl-3,6-bis(2-(1,8-naphthyl)vinyl)-carbazole (material 2) and 9-butyl-3,6- bis(2-(quinolin)vinyl)-carbazole (material 3). Their one photon properties including linear absorption spectra, fluorescence emission spectra, and fluorescence quantum yields are studied. The fluorescence excited by 120 fs pulse at 800 nm Ti: sapphire laser operating at 1 kHz repetition rate with different incident powers of 9-butyl-3-(2-(quinolin) vinyl)-carbazole (material 3) was investigated, and two-photon absorption cross-sections has been obtained. It is shown that material 3 containing quinoline rings as electron acceptor with symmetric structure exhibit high two-photon absorption activity. The result implies that material 3 (9-butyl-3-(2-(quinolin) vinyl)-carbazole) is a good candidate as a promising recording material for super-high-density two-photon absorption (TPA) three-dimensional (3D) optical data storage. The influence of chemical structure of the materials on the optical properties is discussed.

  20. Reduction of the Work Function of Gold by N-Heterocyclic Carbenes

    Kim, Hye Kyung

    2017-04-12

    N-Heterocyclic carbenes (NHCs) bind strongly to gold and other metals. This work experimentally probes the effect of NHCs on the work function (WF) of gold for the first time, theoretically analyzes the origin of this effect, and examines the effectiveness of NHC-modified gold as an electron-injecting electrode. UV photoelectron spectroscopy shows the WF of planar gold is reduced by nearly 2 eV to values of 3.3–3.5 eV. This effect is seen for NHCs with various heterocyclic cores, and with either small or large N,N′-substituents. DFT calculations indicate the WF reduction results from both the interface dipole formed between the NHC and the gold and from the NHC molecular dipole. For N,N′-diisopropyl-NHCs, an important contributor to the former is charge transfer associated with coordination of the carbene carbon atom to gold. In contrast, the carbene carbon of N,N′-2,6-diisopropylphenyl-NHCs is not covalently bound to gold, resulting in a lower interface dipole; however, a larger molecular dipole partially compensates for this. Single-layer C60 diodes with NHC-modified gold as the bottom electrode demonstrate high rectification ratios and show that these electrodes can act as effective electron-injecting contacts, suggesting they may be useful for a variety of materials applications.

  1. Masked N-Heterocyclic Carbene-Catalyzed Alkylation of Phenols with Organic Carbonates.

    Lui, Matthew Y; Yuen, Alexander K L; Masters, Anthony F; Maschmeyer, Thomas

    2016-09-08

    An easily prepared masked N-heterocyclic carbene, 1,3-dimethylimidazolium-2-carboxylate (DMI-CO2 ), was investigated as a "green" and inexpensive organocatalyst for the alkylation of phenols. The process made use of various low-toxicity and renewable alkylating agents, such as dimethyl- and diethyl carbonate, in a focused microwave reactor. DMI-CO2 was found to be a very active catalyst and excellent yields of a range of aryl alkyl ethers were obtained under relatively benign conditions. The observed difference in the conversion behavior of phenol methylation, in the presence of either the carbene or 1,8-diazabicycloundec-7-ene (DBU) catalyst, was rationalized on the basis of mechanistic investigations. The primary mode of action for the N-heterocyclic carbene is nucleophilic catalysis. Activation of the dialkyl carbonate electrophile results in concomitant evolution of an organo-soluble alkoxide, which deprotonates the phenolic starting material. In contrast, DBU is initially protonated by the phenol and thus consumed. Subsequent regeneration and participation in nucleophilic catalysis only becomes significant after some phenolate alkylation occurs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Heterocyclic Naphthalimides as New Skeleton Structure of Compounds with Increasingly Expanding Relational Medicinal Applications.

    Gong, Huo-Hui; Addla, Dinesh; Lv, Jing-Song; Zhou, Cheng-He

    2016-01-01

    Naphthalimide compounds are an important type of nitrogen-containing aromatic heterocycles with cyclic double imides and the naphthalene framework. This π-deficient large conjugated planar structure enables naphthalimide derivatives to readily interact with various biological cations, anions, small molecules and macromolecules such as DNAs, enzymes and recetors in living organism via noncovalent bonds, therefore exhibiting extensive potentiality in relatively medicinal applications. Currently, some naphthalimides as anticancer agents have entered into clinical trials and other naphthalimide-based medicinal developments as potential drugs for treatment of various diseases are actively and unprecedentedly expanding. Naphthalimide-derived artificial ion receptors, fluorescent probes and cell imaging agents are being overwhelmingly investigated and have a diversity of potential applications in real-time detecting ions and biomolecules, understanding biological processes and determining pharmacological and pharmacokinetic properties. All the above mentions have strongly implied that naphthalimide-based derivatives as new skeleton structure of compounds possess increasingly expanding relational medicinal applications, and the related research is becoming a quite attractive active topic and newly rising highlight. Combining with our research and referring other works from literature, this work systematically reviews the current research and development of heterocyclic naphthalimides as anticancer, antibacterial, antifungal, antiviral, anti-inflammatory, antidepressant agents as well as artificial cation and anion receptors, diagnostic agents and pathologic probes, and cell imaging agents for biologically important species. Some rational design strategies, structure-activity relationships and action mechanisms are discussed. The perspectives of the future development of naphthalimide-based medicinal chemistry are also presented.

  3. Recent advances in the research of heterocyclic compounds as antitubercular agents.

    Yan, Mi; Ma, Shutao

    2012-12-01

    Tuberculosis (TB) is a major health problem, with approximately one-third of the world's population infected with Mycobacterium tuberculosis, eight million people in the active disease state, and two million dying annually. Furthermore, the prevalence of TB/HIV co-infection, and the emergence of multidrug-resistant tuberculosis (MDR-TB) and extensively drug-resistant tuberculosis (XDR-TB) have further aggravated the spread of this disease and thus mortality by it. There is an urgent need for novel antitubercular agents with improved properties, such as lower toxicity, shortened duration of therapy, rapid bactericidal action, and enhanced activity against MDR strains. Fortunately, a number of new potential antitubercular candidate drugs with heterocyclic rings, which are most likely to be effective against resistant strains, have entered clinical trials in recent years. This review highlights recent advances in the research of novel heterocyclic compounds, with particular focus on their antimycobacterial activity, mechanisms of action, toxicity, and structure-activity relationships (SARs). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Biological Screening of Newly Synthesized BIAN N-Heterocyclic Gold Carbene Complexes in Zebrafish Embryos

    Farooq, Muhammad; Abu Taha, Nael; Butorac, Rachel R.; Evans, Daniel Anthony; Elzatahry, Ahmed A.; Elsayed, Elsayed Ahmed; Wadaan, Mohammad A. M.; Al-Deyab, Salem S.; Cowley, Alan H.

    2015-01-01

    N-Heterocyclic carbene (NHC) metal complexes possess diverse biological activities but have yet to be extensively explored as potential chemotherapeutic agents. We have previously reported the synthesis of a new class of NHC metal complexes N-heterocyclic with acetate [IPr(BIAN)AuOAc] and chloride [IPr(BIAN)AuCl] ligands. In the experiments reported herein, the zebrafish embryos were exposed to serial dilutions of each of these complexes for 10–12 h. One hundred percent mortality was observed at concentrations ≥50 µM. At sub-lethal concentrations (10–30 µM), both compounds influenced zebrafish embryonic development. However, quite diverse categories of abnormalities were found in exposed embryos with each compound. Severe brain deformation and notochord degeneration were evident in the case of [IPr(BIAN)AuOAc]. The zebrafish embryos treated with [IPr(BIAN)AuCl] exhibited stunted growth and consequently had smaller body sizes. A depletion of 30%–40% glutathione was detected in the treated embryos, which could account for one of the possible mechanism of neurotoxicity. The fact that these compounds are capable of both affecting the growth and also compromising antioxidant systems by elevating intracellular ROS production implies that they could play an important role as a new breed of therapeutic molecules. PMID:26501273

  5. Differential specificity in the glomerular response profiles for alicyclic, bicyclic and heterocyclic odorants

    Johnson, Brett A.; Xu, Zhe; Pancoast, Paige; Kwok, Jennifer; Ong, Joan; Leon, Michael

    2008-01-01

    As part of our ongoing effort to relate stimulus to response in the olfactory system, we tested the hypothesis that the unique chemical structures and odors of various cyclic odorants would be associated with unique spatial response patterns in the glomerular layer of the rat olfactory bulb. To this end, rats were exposed to sets of odorants including monocyclic hydrocarbons, bicyclic compounds, and various heterocyclic structures containing oxygen or nitrogen in the ring. Relative activity across the entire layer was assessed by mapping uptake of 2-deoxyglucose into anatomically standardized data matrices. Whereas monocyclic hydrocarbons evoked patterns similar to those evoked by open-chained hydrocarbon odorants, a set of bicyclic compounds with structures and odors similar to camphor evoked uptake in paired ventral domains not previously associated with any other odorant chemical structures. Despite their unique odors as judged by humans, heterocyclic odorants either evoked uptake in previously characterized areas corresponding to their functional groups or stimulated weak or patchy patterns involving isolated glomeruli. While the patchiness of the patterns may be partly related to the rigidity of the compounds, which would be expected to restrict their interactions to only a few receptors, the weakness of the patterns suggests the possibility of species-specific odorant representations. We conclude that whereas some of the novel cyclic structures indeed were represented by unique patterns in the rat bulb, other unique structures were poorly represented, even when they evoked intense and unique odors in humans. PMID:16958095

  6. Reduction of the Work Function of Gold by N-Heterocyclic Carbenes

    Kim, Hye Kyung; Hyla, Alexander; Winget, Paul; Li, Hong; Wyss, Chelsea M.; Jordan, Abraham J.; Larrain, Felipe A.; Sadighi, Joseph P.; Fuentes-Hernandez, Canek; Kippelen, Bernard; Bredas, Jean-Luc; Barlow, Stephen; Marder, Seth R.

    2017-01-01

    N-Heterocyclic carbenes (NHCs) bind strongly to gold and other metals. This work experimentally probes the effect of NHCs on the work function (WF) of gold for the first time, theoretically analyzes the origin of this effect, and examines the effectiveness of NHC-modified gold as an electron-injecting electrode. UV photoelectron spectroscopy shows the WF of planar gold is reduced by nearly 2 eV to values of 3.3–3.5 eV. This effect is seen for NHCs with various heterocyclic cores, and with either small or large N,N′-substituents. DFT calculations indicate the WF reduction results from both the interface dipole formed between the NHC and the gold and from the NHC molecular dipole. For N,N′-diisopropyl-NHCs, an important contributor to the former is charge transfer associated with coordination of the carbene carbon atom to gold. In contrast, the carbene carbon of N,N′-2,6-diisopropylphenyl-NHCs is not covalently bound to gold, resulting in a lower interface dipole; however, a larger molecular dipole partially compensates for this. Single-layer C60 diodes with NHC-modified gold as the bottom electrode demonstrate high rectification ratios and show that these electrodes can act as effective electron-injecting contacts, suggesting they may be useful for a variety of materials applications.

  7. The pH-influenced PET processes between pyronine and different heterocycles.

    Yang, Ling; Niu, Jin-Yun; Sun, Ru; Xu, Yu-Jie; Ge, Jian-Feng

    2017-10-11

    The OFF-ON and ON-OFF type pH probes based on rosamine were designed by using the relative electron densities between pyronine and various linked heterocycles. Probe 1a with an indole-pyronine skeleton gave an OFF-ON pH response (pK a = 1.41) with decreasing pH, and the relative fluorescence intensity increased 15-fold, while probe 1b with an imidazole-pyronine skeleton did not give an ON-OFF response to different pH values. When pyronine was connected with a quinolinyl group, i.e., probes 1c-d, the red emission (around 575-800 nm) gave a monotonous ON-OFF pH response (pK a = 3.26 and 2.62, respectively) with decreasing pH. The relative fluorescence intensities decreased 263- and 46-fold, respectively. Changes in the electron donating abilities of the nitrogen containing heterocycles were used to explain variations in PET processes within the probes, and their pH-dependent PET mechanisms were verified using time-dependent density functional theory calculations. Confocal fluorescence imaging was also used to evaluate the potential biomedical application of probes 1a-d. Ultimately, probe 1d with an appropriate pK a value and good biocompatibility showed lysosome targeting ability.

  8. Réflexions sur la science contemporaine

    Darriulat, Pierre

    2007-01-01

    L'auteur y brosse à grands traits un tableau de la science contemporaine : réductionnisme, déterminisme, abstraction, méthodes, mécanismes de validation et interactions entre observation et théorie... ainsi qu'un portrait de ses artisans et une critique des stéréotypes les plus courants (philistin, iconoclaste, apprenti sorcier...) L'accent est mis sur le fait que la science, dont une des missions consiste à dénoncer les illusions du sens commun, ne poursuit pas une quête de vérité absolue mais se contente aujourd'hui d'une vérité simplement meilleure que celle d'hier. La circularité de la science lui interdit de répondre à des questions essentielles comme «Pourquoi ce monde plutôt que rien ?» Pour tenter d'y répondre, le physicien Pierre Darriulat entreprend, avec candeur et bienveillance, un voyage chez les philosophes. Comment la métaphysique s'évade-t-elle du cercle ? Quelle connaissance autre que scientifique nous propose-t-elle ? La circularité condamnant la science au silence...

  9. Cyclopentadienyl molybdenum(II/VI) N-heterocyclic carbene complexes: Synthesis, structure, and reactivity under oxidative conditions

    Li, Shenyu; Kee, Choonwee; Huang, Kuo-Wei; Hor, Andy Sum Andy; Zhao, Jin

    2010-01-01

    A series of N-heterocyclic carbene (NHC) complexes CpMo(CO) 2(NHC)X (NHC = IMe = 1,3-dimethylimidazol-2-ylidene, X = Br, 1; NHC = 1,3-dipropylimidazol-2-ylidene, X = Br, 2; NHC = IMes = 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, X = Br, 3

  10. N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

    Wang, Ying; Du, Guang Fen; Xing, Fen; Huang, Kuo-Wei; Dai, Bin; He, Lin

    2015-01-01

    N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Synthesis, characterization, and reactivity of furan- and thiophene-functionalized bis(n-heterocyclic carbene) complexes of iron(II)

    Rieb, Julia; Raba, Andreas; Haslinger, Stefan; Kaspar, Manuel; Pö thig, Alexander; Cokoja, Mirza; Basset, Jean-Marie; Kü hn, Fritz

    2014-01-01

    The synthesis of iron(II) complexes bearing new heteroatom-functionalized methylene-bridged bis(N-heterocyclic carbene) ligands is reported. All complexes are characterized by single-crystal X-ray diffraction (SC-XRD), nuclear magnetic resonance

  12. Content of heterocyclic amines and polycyclic aromatic hydrocarbons in pork, beef and chicken barbecued at home by Danish consumers

    Aaslyng, Margit D.; Duedahl-Olesen, Lene; Jensen, Kirsten

    2013-01-01

    It is a well-known fact that, when meat is barbecued, several harmful components, including heterocyclic amines (HCA) and polycyclic aromatic hydrocarbons (PAH), may be formed. The aim of this study was to determine the HCA and PAH content in meat (pork, chicken and beef) when barbecued at home...

  13. Optimized Syntheses of Cyclopentadienyl Nickel Chloride Compounds Containing "N"-Heterocyclic Carbene Ligands for Short Laboratory Periods

    Cooke, Jason; Lightbody, Owen C.

    2011-01-01

    Experiments are described for the preparation of imidazolium chloride precursors to "N"-heterocyclic carbenes and their cyclopentadienyl nickel chloride derivatives. The syntheses have been optimized for second- and third-year undergraduate laboratories that have a maximum programmed length of three hours per week. The experiments are flexible and…

  14. Synthesis of Heterocycles through a Ruthenium‐Catalyzed Tandem Ring‐Closing Metathesis/Isomerization/N‐Acyliminium Cyclization Sequence

    Ascic, Erhad; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

    2011-01-01

    Tandem bicycle: In the title reaction double bonds created during ring-closing metathesis isomerize to generate reactive iminium intermediates that undergo intramolecular cyclization reactions with tethered heteroatom and carbon nucleophiles. In this way, a series of biologically interesting hete...... heterocyclic compounds can be made, including a known precursor for the total synthesis of the antiparasitic natural product harmicine....

  15. The structure of active centers and the kinetic isotopic effect in the ionic polymerization of heterocyclic compounds

    Ponomarienko, W.A.; Berman, E.L.

    1979-01-01

    The method of kinetic isotopic effect has been applied to the elucidation of the structure of the active growth centres in the polymerization of some selected heterocyclic compounds. The cationic polymerization of ehtylene oxide, tetrahydrofuran and 1.3-dioxolane as well as the anionic and coordination polymerization of ethylene oxide have been discussed. (author)

  16. Atmospheric CO2 promoted synthesis of N-containing heterocycles over B(C6F5)3 catalyst

    Xiang Gao; Bo Yu; Qingqing Mei; Zhenzhen Yang; Yanfei Zhao; Hongye Zhang; Leiduan Hao, Zhimin Liu

    2016-01-01

    B(C 6 F 5 ) 3 combined with atmospheric CO 2 was found to be highly effective for the cyclization of ortho substituted aniline derivatives with N,N-dimethylformamide (DMF), and a series of N-containing heterocycles including benzothiazoles, benzimidazoles, quinazolinone and benzoxazole were obtained in good to excellent yields. (authors)

  17. MACROMOLECULAR ADDUCT FORMATION AND METABOLISM OF HETEROCYCLIC AMINES IN HUMANS AND RODENTS AT LOW DOSES. (R825280)

    Abstract2-Amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) are heterocyclic amines formed during the cooking of meat and fish. Both are genotoxic in a number of test systems and are carcinogen...

  18. N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

    Wang, Ying

    2015-10-15

    N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. The effect of heterocyclic S,S’-ligands on the electrochemical properties of some cobalt(III complexes in acid

    V. M. JOVANOVIC

    2005-02-01

    Full Text Available Eight mixed-ligand cobalt(III complexes with the macrocyclic amine 1,4,8,11-tetraazacyclotetradecane (cyclam and a heterocyclic dithiocarbamate (Rdtc- i.e., morpholine- (Morphdtc, thiomorpholine- (Timdtc, piperazine- (Pzdtc, N-methylpiperazine-(Mepzdtc, piperidine- (Pipdtc, 2-, 3- or 4-methylpiperidine- (2-, 3- and 4-Mepipdtc carbodithionato-S,S ions, of the general formula [Co(cyclamRdtc](ClO42, were investigated in deoxygenated 0.1MHClO4 solutions. Cyclic voltammetry data at a glassy carbon (GC electrode demonstrate a redox reaction of cobalt(III from the complexes at potentials strongly influenced by the presence of different heterocyclic Rdtc- ligands. In this respect, the complexes were separated into two groups: the first, with a heteroatom O, S or N in the heterocyclic ring, and the second, with a methyl group on the piperidine ring of the Rdtc- ligand. Anodic polarization of an Fe electrode in the presence of the complexes shows their influence not only on the dissolution of iron but also on the hydrogen evolution reactions and on this basis complexes the complexes could be divided into the same two groups. It was found that the weaker the inhibiting effect of the free heterocyclic amines is, the significantly higher is the efficiency of the corresponding complexes.

  20. Synthesis and Properties of Chelating N-Heterocyclic Carbene Rhodium(I) Complexes: Synthetic Experiments in Current Organometallic Chemistry

    Mata, Jose A.; Poyatos, Macarena; Mas-Marza, Elena

    2011-01-01

    The preparation and characterization of two air-stable Rh(I) complexes bearing a chelating N-heterocyclic carbene (NHC) ligand is described. The synthesis involves the preparation of a Ag(I)-NHC complex and its use as carbene transfer agent to a Rh(I) precursor. The so obtained complex can be further reacted with carbon monoxide to give the…

  1. Synthesis and Antimicrobial Studies of New Series of Pyrazoline Bearing Bis-Heterocycles via 1,3-Dipolar Cycloaddition Reactions

    B. Jayashankara

    2008-01-01

    Full Text Available Biologically interesting bis-heterocycles bearing pyrazoline and imidazole moieties have been synthesized. 1H NMR, 13C NMR, IR and elemental analyses characterized the newly synthesized compounds. All the synthesized compounds were evaluated for their antimicrobial activity and were compared with the standard drugs. All the compounds demonstrated potent to weak antimicrobial activity.

  2. 2107-IJBCS-Article-Hamidou Zeinabou

    hp

    Peu de données existent sur la contribution en azote des légumineuses, et leurs impacts en présence des fumures sur la nutrition azotée des céréales. Ainsi, pour évaluer les effets du niébé et des fumures organo-minérales sur la nutrition azotée et les rendements du mil subséquent, une expérimentation a été conduite de ...

  3. Kir6.2 activation by sulfonylurea receptors: a different mechanism of action for SUR1 and SUR2A subunits via the same residues

    Principalli, Maria A; Dupuis, Julien P; Moreau, Christophe J; Vivaudou, Michel; Revilloud, Jean

    2015-01-01

    ATP-sensitive potassium channels (K-ATP channels) play a key role in adjusting the membrane potential to the metabolic state of cells. They result from the unique combination of two proteins: the sulfonylurea receptor (SUR), an ATP-binding cassette (ABC) protein, and the inward rectifier K+ channel Kir6.2. Both subunits associate to form a heterooctamer (4 SUR/4 Kir6.2). SUR modulates channel gating in response to the binding of nucleotides or drugs and Kir6.2 conducts potassium ions. The activity of K-ATP channels varies with their localization. In pancreatic β-cells, SUR1/Kir6.2 channels are partly active at rest while in cardiomyocytes SUR2A/Kir6.2 channels are mostly closed. This divergence of function could be related to differences in the interaction of SUR1 and SUR2A with Kir6.2. Three residues (E1305, I1310, L1313) located in the linker region between transmembrane domain 2 and nucleotide-binding domain 2 of SUR2A were previously found to be involved in the activation pathway linking binding of openers onto SUR2A and channel opening. To determine the role of the equivalent residues in the SUR1 isoform, we designed chimeras between SUR1 and the ABC transporter multidrug resistance-associated protein 1 (MRP1), and used patch clamp recordings on Xenopus oocytes to assess the functionality of SUR1/MRP1 chimeric K-ATP channels. Our results reveal that the same residues in SUR1 and SUR2A are involved in the functional association with Kir6.2, but they display unexpected side-chain specificities which could account for the contrasted properties of pancreatic and cardiac K-ATP channels. PMID:26416970

  4. Normal-phase liquid chromatography retention behavior of polycyclic aromatic sulfur heterocycles and alkyl-substituted polycyclic aromatic sulfur heterocycle isomers on an aminopropyl stationary phase.

    Wilson, Walter B; Hayes, Hugh V; Sander, Lane C; Campiglia, Andres D; Wise, Stephen A

    2018-02-01

    Retention indices for 67 polycyclic aromatic sulfur heterocycles (PASHs) and 80 alkyl-substituted PASHs were determined using normal-phase liquid chromatography (NPLC) on an aminopropyl (NH 2 ) stationary phase. The retention behavior of PASH on the NH 2 phase is correlated with the number of aromatic carbon atoms and two structural characteristics have a significant influence on their retention: non-planarity (thickness, T) and the position of the sulfur atom in the bay-region of the structure. Correlations between solute retention on the NH 2 phase and T of PASHs were investigated for three cata-condensed (cata-) PASH isomer groups: (a) 13 four-ring molecular mass (MM) 234 Da cata-PASHs, (b) 20 five-ring MM 284 Da cata-PASHs, and (c) 12 six-ring MM 334 Da cata-PASHs. Correlation coefficients ranged from r = -0.49 (MM 234 Da) to r = -0.65 (MM 334 Da), which were significantly lower than structurally similar PAH isomer groups (r = -0.70 to r = -0.99). The NPLC retention behavior of the PASHs are compared to similar results for PAHs.

  5. Synthesis, biological evaluation and SAR analysis of novel poly-heterocyclic compounds containing pyridylpyrazole group.

    Wang, Bao-Lei; Zhu, Hong-Wei; Li, Zheng-Ming; Wang, Li-Zhong; Zhang, Xiao; Xiong, Li-Xia; Song, Hai-Bin

    2018-03-01

    In recent years, pyridylpyrazole derivatives, such as pyridylpyrazole-containing anthranilic diamide have attracted much attention by virtue of their useful insecticidal properties and unique action mode. Moreover, some pyridylpyrazole-containing compounds have also been found to possess significant fungicidal activities. With the aim of discovering new bioactive agrochemicals for crop protection, a series of poly-heterocyclic compounds containing pyridylpyrazole and aziridine, or β-lactam, or thiazolinone moieties were synthesized. A series of pyridylpyrazole-containing poly-heterocyclic compounds were obtained, and confirmed through IR, 1 H NMR, 13 C NMR, HRMS and elemental analysis. The crystalline structure of 4-(3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)-3-chloro-1-mesitylazetidin-2-one (compound 13f) was determined to further illustrate a trans- configuration of the β-lactam motif. In addition, bioassays showed that most of these new compounds exhibited modest insecticidal activity towards Mythimna separate Walker at 200 µg mL -1 . Some of the compounds displayed excellent fungicidal activity towards some plant fungi, including Cercospora arachidicola (13j: EC 50 = 14.5 µg mL -1 ), Physalospora piricola (12d and 13d: EC 50 = 10.5 and 9.70 µg mL -1 ), Alternaria solani Sorauer (13j: EC 50 = 7.29 µg mL -1 ), Puccinia sorghi Schw. (13d: control efficacy 99.0 ± 2.1% at 200 µg mL -1 ) and Erysiphe graminis (14d: control efficacy 95.0 ± 1.4% at 200 µg mL -1 ). Compounds 12b-12e, 13a, 13d, 13f, 13j, 13 k and 14d could be considered potential fungicidal lead compounds to do further structural optimization. The structure-activity relationship analysis in this study brings some new understanding to the biological activities of N-pyridylpyrazole-containing compounds, and provides important information for the research and development of novel agricultural fungicides with poly-heterocyclic structures. © 2017 Society of Chemical Industry. © 2017 Society

  6. Exploring the novel heterocyclic derivatives as lead molecules for design and development of potent anticancer agents.

    Azad, Iqbal; Nasibullah, Malik; Khan, Tahmeena; Hassan, Firoj; Akhter, Yusuf

    2018-05-01

    This paper deals with in silico evaluation of newly proposed heterocyclic derivatives in search of potential anticancer activity. Best possible drug candidates have been proposed using a rational approach employing a pipeline of computational techniques namely MetaPrint2D prediction, molinspiration, cheminformatics, Osiris Data warrior, AutoDock and iGEMDOCK. Lazar toxicity prediction, AdmetSAR predictions, and targeted docking studies were also performed. 27 heterocyclic derivatives were selected for bioactivity prediction and drug likeness score on the basis of Lipinski's rule, Viber rule, Ghose filter, leadlikeness and Pan Assay Interference Compounds (PAINS) rule. Bufuralol, Sunitinib, and Doxorubicin were selected as reference standard drug for the comparison of molecular descriptors and docking. Bufuralol is a known non-selective adreno-receptor blocking agent. Studies showed that beta blockers are also used against different types of cancers. Sunitinib is well known Food and Drug administration (FDA) approved pyrrole containing tyrosine kinase inhibitor and our proposed molecules possess similarities with both drug and doxorubicin is another moiety having anticancer activity. All heterocyclic derivatives were found to obey the drug filters except standard drug Doxorubicin. Bioactivity score of the compounds was predicted for drug targets including enzymes, nuclear receptors, kinase inhibitors, G protein-coupled receptor (GPCR) ligands and ion channel modulators. Absorption, distribution, metabolism and toxicity (ADMET) prediction of all proposed compound showed good Blood-brain barrier (BBB) penetration, Human intestinal absorption (HIA), Caco-2 cell permeability except compound-11 and was found to have no AdmetSAR toxicity as well as carcinogenic effect. Compounds 1-9 were slightly mutagenic while compound 2, 11, 20 and 21 showed carcinogenic effect according to Lazar toxicity prediction. Rests of the compounds were predicted to have no side effect

  7. Nitrogen Heterocycles in Miller-Urey Spark-Discharge Mixtures: Using Chemical Trends to Elucidate Plausible Pre-RNAs on the Early Earth

    Rodriguez, L. E.; House, C. H.; Callahan, M. P.

    2017-07-01

    We incubated 53 nitrogen heterocycles with spark-discharge mixtures and found that they react with only a handful of nitriles to yield adducts that may polymerize. Whether these adducts can form a monomer of Peptide Nucleic Acid was investigated.

  8. Solid‐Phase Synthesis of Structurally Diverse Heterocycles by an Amide–Ketone Condensation/N‐Acyliminium Pictet–Spengler Sequence

    Komnatnyy, Vitaly V.; Givskov, Michael Christian; Nielsen, Thomas Eiland

    2012-01-01

    An efficient approach for the solid‐phase synthesis of structurally diverse heterocyclic compounds is presented. Under acidic reaction conditions, peptidic levulinamides undergo intramolecular ketone–amide condensation reactions to form cyclic N‐acyliminium intermediates. In the presence...

  9. Pyrolysis of high-ash sewage sludge in a circulating fluidized bed reactor for production of liquids rich in heterocyclic nitrogenated compounds.

    Zuo, Wu; Jin, Baosheng; Huang, Yaji; Sun, Yu; Li, Rui; Jia, Jiqiang

    2013-01-01

    A circulating fluidized bed reactor was used for pyrolyzing sewage sludge with a high ash content to produce liquids rich in heterocyclic nitrogenated compounds. GC/MS and FTIR analyses showed that heterocyclic nitrogenated compounds and hydrocarbons made up 38.5-61.21% and 2.24-17.48% of the pyrolysis liquids, respectively. A fluidized gas velocity of 1.13 m/s, a sludge feed rate of 10.78 kg/h and a particle size of 1-2mm promoted heterocyclic nitrogenated compound production. Utilizing heterocyclic nitrogenated compounds as chemical feedstock could be a way for offsetting the cost of sewage sludge treatment. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. N- AND O-HETEROCYCLES PRODUCED FROM THE IRRADIATION OF BENZENE AND NAPHTHALENE IN H2O/NH3-CONTAINING ICES

    Materese, Christopher K.; Nuevo, Michel; Sandford, Scott A.

    2015-01-01

    Aromatic heterocyclic molecules are an important class of molecules of astrophysical and biological significance that include pyridine, pyrimidine, and their derivatives. Such compounds are believed to exist in interstellar and circumstellar environments, though they have never been observed in the gas phase. Regardless of their presence in the gas phase in space, numerous heterocycles have been reported in carbonaceous meteorites, which indicates that they are formed under astrophysical conditions. The experimental work described here shows that N- and O-heterocyclic molecules can form from the ultraviolet (UV) irradiation of the homocyclic aromatic molecules benzene (C 6 H 6 ) or naphthalene (C 10 H 8 ) mixed in ices containing H 2 O and NH 3 . This represents an alternative way to generate aromatic heterocycles to those considered before and may have important implications for astrochemistry and astrobiology

  11. N- AND O-HETEROCYCLES PRODUCED FROM THE IRRADIATION OF BENZENE AND NAPHTHALENE IN H{sub 2}O/NH{sub 3}-CONTAINING ICES

    Materese, Christopher K.; Nuevo, Michel; Sandford, Scott A., E-mail: christopher.k.materese@nasa.gov [NASA Ames Research Center, Moffett Field, CA 94035 (United States)

    2015-02-20

    Aromatic heterocyclic molecules are an important class of molecules of astrophysical and biological significance that include pyridine, pyrimidine, and their derivatives. Such compounds are believed to exist in interstellar and circumstellar environments, though they have never been observed in the gas phase. Regardless of their presence in the gas phase in space, numerous heterocycles have been reported in carbonaceous meteorites, which indicates that they are formed under astrophysical conditions. The experimental work described here shows that N- and O-heterocyclic molecules can form from the ultraviolet (UV) irradiation of the homocyclic aromatic molecules benzene (C{sub 6}H{sub 6}) or naphthalene (C{sub 10}H{sub 8}) mixed in ices containing H{sub 2}O and NH{sub 3}. This represents an alternative way to generate aromatic heterocycles to those considered before and may have important implications for astrochemistry and astrobiology.

  12. Synthesis and Reactions of Five-Membered Heterocycles Using Phase Transfer Catalyst (PTC Techniques

    Ahmed M. El-Sayed

    2014-01-01

    Full Text Available Phase transfer catalysts (PTCs have been widely used for the synthesis of organic compounds particularly in both liquid-liquid and solid-liquid heterogeneous reaction mixtures. They are known to accelerate reaction rates by facilitating formation of interphase transfer of species and making reactions between reagents in two immiscible phases possible. Application of PTC instead of traditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment. On the basis of numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many active intermediates. In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compounds and their multifused rings.

  13. Quantum chemical modeling of the inhibition mechanism of monoamine oxidase by oxazolidinone and analogous heterocyclic compounds.

    Erdem, Safiye Sağ; Özpınar, Gül Altınbaş; Boz, Ümüt

    2014-02-01

    Monoamine oxidase (MAO, EC 1.4.3.4) is responsible from the oxidation of a variety of amine neurotransmitters. MAO inhibitors are used for the treatment of depression or Parkinson's disease. They also inhibit the catabolism of dietary amines. According to one hypothesis, inactivation results from the formation of a covalent adduct to a cysteine residue in the enzyme. If the adduct is stable enough, the enzyme is inhibited for a long time. After a while, enzyme can turn to its active form as a result of adduct breakdown by β-elimination. In this study, the proposed inactivation mechanism was modeled and tested by quantum chemical calculations. Eight heterocyclic methylthioamine derivatives were selected to represent the proposed covalent adducts. Activation energies related to their β-elimination reactions were calculated using ab initio and density functional theory methods. Calculated activation energies were in good agreement with the relative stabilities of the hypothetical adducts predicted in the literature by enzyme inactivation measurements.

  14. Rapid trifluoromethylation and perfluoroalkylation of five-membered heterocycles by photoredox catalysis in continuous flow.

    Straathof, Natan J W; Gemoets, Hannes P L; Wang, Xiao; Schouten, Jaap C; Hessel, Volker; Noël, Timothy

    2014-06-01

    Trifluoromethylated and perfluoroalkylated heterocycles are important building blocks for the synthesis of numerous pharmaceutical products, agrochemicals and are widely applied in material sciences. To date, trifluoromethylated and perfluoroalkylated hetero-aromatic systems can be prepared utilizing visible light photoredox catalysis methodologies in batch. While several limitations are associated with these batch protocols, the application of microflow technology could greatly enhance and intensify these reactions. A simple and straightforward photocatalytic trifluoromethylation and perfluoroalkylation method has been developed in continuous microflow, using commercially available photocatalysts and microflow components. A selection of five-membered hetero-aromatics were successfully trifluoromethylated (12 examples) and perfluoroalkylated (5 examples) within several minutes (8-20 min). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. SYNTHESIS AND STUDY OF HALOGENATED BENZYLAMIDES OF SOME ISOCYCLIC AND HETEROCYCLIC ACIDS AS POTENTIAL ANTICONVULSANTS.

    Strupińska, Marzanna; Rostafińska-Suchar, Grażyna; Pirianowicz-Chaber, Elżbieta; Grabczuk, Mateusz; Józwenko, Magdalena; Kowalczyk, Hubert; Szuba, Joanna; Wójcicka, Monika; Chen, Tracy; Mazurek, Aleksander P

    2015-01-01

    A series of potential anticonvulsants have been synthesized. There are eight fluorobenzylamides and three chlorobenzylamides of isocyclic or heterocyclic acids. Two not halogenated benzylamides were also synthesized to compare the effect of halogenation. The aim of the research performed was to evaluate whether halogenation of the mother structure is able to improve its anticonvulsant activity. The compounds were tested in Anticonvulsant Screening Project (ASP) of Antiepileptic Drug Development Program (ADDP) of NIH. Compound 1 showed MES ED50 = 80.32 mg/kg, PI = 3.16. Compound 7 showed CKM ED50 = 56.72 mg/kg. Compound 8 showed MES ED50 = 34.23 mg/kg and scPTZ ED50 > 300 mg/kg, PI = 8.53.Compound 13 showed 6Hz ED50 = 78.96, PI = 3.37. The results indicate that fluorination does not improve activity, whereas chlorination in our experiment even reduces it.

  16. PRESSURE EFFECTS IN POLYCYCLIC AROMATIC NITROGENATED HETEROCYCLES (PANHs): DIAGNOSTIC QUALITIES AND COSMOBAROMETRY POTENTIAL

    Montgomery, Wren; Sephton, Mark A., E-mail: w.montgomery@imperial.ac.uk [Impacts and Astromaterials Research Centre, Department of Earth Science and Engineering, Imperial College London SW7 2AZ (United Kingdom)

    2016-03-01

    The influence of polycyclic aromatic nitrogen heterocycles (PANHs), which have been suggested as contributors to the interstellar IR emission bands, on interstellar emission features is difficult to constrain because their infrared characteristics are strongly similar to those for polycyclic aromatic hydrocarbons (PAHs). One possible solution is to seek a means of visualizing the presence of PANHs that provides information that is distinct from that for PAHs. Although PANHs and PAHs have similar infrared characteristics in many settings, this relationship may not be universally maintained. We have used in situ high-pressure synchrotron-source Fourier transform infrared spectroscopy to determine that the responses of two representative molecules, acridine and anthracene, differ at high pressures (>ca. 1 GPa). Because there are a number of high-pressure environments that can be remotely observed by infrared spectroscopy, they represent a potential to glimpse the distribution of PANHs across the cosmos.

  17. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    Zhao, Changgui

    2018-02-05

    Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations.

  18. Does the Intramolecular Hydrogen Bond Affect the Spectroscopic Properties of Bicyclic Diazole Heterocycles?

    Paweł Misiak

    2018-01-01

    Full Text Available The formation of an intramolecular hydrogen bond in pyrrolo[1,2-a]pyrazin-1(2H-one bicyclic diazoles was analyzed, and the influence of N-substitution on HB formation is discussed in this study. B3LYP/aug-cc-pVDZ calculations were performed for the diazole, and the quantum theory of atoms in molecules (QTAIM approach as well as the natural bond orbital (NBO method was applied to analyze the strength of this interaction. It was found that the intramolecular hydrogen bond that closes an extra ring between the C=O proton acceptor group and the CH proton donor, that is, C=O⋯H–C, influences the spectroscopic properties of pyrrolopyrazine bicyclic diazoles, particularly the carbonyl frequencies. The influence of N-substitution on the aromaticity of heterocyclic rings is also discussed in this report.

  19. Ballbot-type motion of N-heterocyclic carbenes on gold surfaces

    Wang, Gaoqiang; Rühling, Andreas; Amirjalayer, Saeed; Knor, Marek; Ernst, Johannes Bruno; Richter, Christian; Gao, Hong-Jun; Timmer, Alexander; Gao, Hong-Ying; Doltsinis, Nikos L.; Glorius, Frank; Fuchs, Harald

    2017-02-01

    Recently, N-heterocyclic carbenes (NHCs) were introduced as alternative anchors for surface modifications and so offered many attractive features, which might render them superior to thiol-based systems. However, little effort has been made to investigate the self-organization process of NHCs on surfaces, an important aspect for the formation of self-assembled monolayers (SAMs), which requires molecular mobility. Based on investigations with scanning tunnelling microscopy and first-principles calculations, we provide an understanding of the microscopic mechanism behind the high mobility observed for NHCs. These NHCs extract a gold atom from the surface, which leads to the formation of an NHC-gold adatom complex that displays a high surface mobility by a ballbot-type motion. Together with their high desorption barrier this enables the formation of ordered and strongly bound SAMs. In addition, this mechanism allows a complementary surface-assisted synthesis of dimeric and hitherto unknown trimeric NHC gold complexes on the surface.

  20. Anoxic degradation of nitrogenous heterocyclic compounds by activated sludge and their active sites.

    Xu, Peng; Han, Hongjun; Zhuang, Haifeng; Hou, Baolin; Jia, Shengyong; Wang, Dexin; Li, Kun; Zhao, Qian

    2015-05-01

    The potential for degradation of five nitrogenous heterocyclic compounds (NHCs), i.e., imidazole, pyridine, indole, quinoline, and carbazole, was investigated under anoxic conditions with acclimated activated sludge. Results showed that NHCs with initial concentration of 50 mg/L could be completely degraded within 60 hr. The degradation of five NHCs was dependent upon the chemical structures with the following sequence: imidazole>pyridine>indole>quinoline>carbazole in terms of their degradation rates. Quantitative structure-biodegradability relationship studies of the five NHCs showed that the anoxic degradation rates were correlated well with highest occupied molecular orbital. Additionally, the active sites of NHCs identified by calculation were confirmed by analysis of intermediates using gas chromatography and mass spectrometry. Copyright © 2015. Published by Elsevier B.V.

  1. Oxygenated heterocyclic compounds to differentiate Citrus spp. essential oils through metabolomic strategies.

    Masson, Jerome; Liberto, Erica; Beolor, Jean-Claude; Brevard, Hugues; Bicchi, Carlo; Rubiolo, Patrizia

    2016-09-01

    This study aimed to characterise and discriminate 44 authenticated commercial samples of citrus essential oils (EO) from seven species (bergamot, lemon, bigarade, orange, mandarin, grapefruit, lime) by analysing the non-volatile oxygenated heterocyclic compounds (OHC) by UHPLC/TOF-HRMS, multivariate data analysis (PCA, PLS-DA) and metabolomic strategies; the OHC fraction includes coumarins, furocoumarins, and polymethoxylated flavonoids. Two different approaches were adopted: (i) targeted profiling based on quantifying 18 furocoumarins and coumarins, some of which are regulated by law, and (ii) targeted fingerprinting based on 140 OHCs reported in citrus essential oils, from which 38 discriminant markers were defined. This approach correctly discriminated the Citrus species; its "sensitivity" to relatively low adulteration rate (10%) was highly satisfactory. The proposed method is complementary to that of analysing the citrus EO volatile part by GC techniques. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Mixed ligand complexes of uranyl lactate with some simple and heterocyclic amines

    Jaiswal, S.R.; Rupainwar, D.C.

    1984-01-01

    Mixed ligand complexes of uranyl lactate with simple and heterocyclic amines having a general formula UO 2 (C 3 H 5 O 3 ).nL.xH 2 O, were prepared, where n=1 and x=1 for L=ethylenediamine (En), dimethyl aniline (DMAn), diethyl amine (DEA), orthophenylenediamine (OPDA), pyridine (Py), 2-picoline(2-Pic), 3-picoline(3-Pic), 4-Picoline(4-Pic), piperidine (Pipy), 2,4-lutidine (2,4 Lut), 2-Aminopyridine (2 APy), quinoline (Quin), isoquinoline (Isoquin) but x=0 for the ligands 2,2'-bipyrldyl (Bipy) and 1,10-phenenthroline (Phen). All the compounds are bright yellow coloured with high decomposition temp. (>200deg) and were characterized by electronic and infrared spectral data. (author)

  3. Utilization of Cyanoacetohydrazide and Oxadiazolyl Acetonitrile in the Synthesis of Some New Cytotoxic Heterocyclic Compounds.

    Shaker, Soheir A; Marzouk, Magda I

    2016-01-29

    A (pyridazinyl)acetate derivative was reacted with thiosemicarbazide and hydrazine hydrate to yield spiropyridazinone and acetohydrazide derivatives, respectively. The acetohydrazide derivative was used as a starting material for synthesizing some new heterocyclic compounds such as oxoindolinylidene, dimethylpyrazolyl, methylpyrazolyl, oxopyrazolyl, cyanoacetylacetohydrazide and oxadiazolylacetonitrile derivatives. The behavior of the cyanoacetylacetohydrazide and oxadiazolylacetonitrile derivatives towards nitrogen and carbon nucleophiles was investigated. The assigned structures of the prepared compounds were elucidated by spectral methods (IR, ¹H-NMR (13)C-NMR and mass spectroscopy). Some of the newly prepared compounds were tested in vitro against a panel of four human tumor cell lines, namely hepatocellular carcinoma (liver) HePG-2, colon cancer HCT-116, human prostate cancer PC3, and mammary gland breast MCF-7. Also they were tested as antioxidants. Almost all of the tested compounds showed satisfactory activity.

  4. Heterocyclic Schiff bases as non toxic antioxidants: Solvent effect, structure activity relationship and mechanism of action

    Shanty, Angamaly Antony; Mohanan, Puzhavoorparambil Velayudhan

    2018-03-01

    Phenolic heterocyclic imine based Schiff bases from Thiophene-2-carboxaldehyde and Pyrrole-2-carboxaldehyde were synthesized and characterized as novel antioxidants. The solvent effects of these Schiff bases were determined and compared with standard antioxidants, BHA employing DPPH assay and ABTS assay. Fixed reaction time and Steady state measurement were used for study. IC50 and EC50 were calculated. Structure-activity relationship revealed that the electron donating group in the phenolic ring increases the activity where as the electron withdrawing moiety decreases the activity. The Schiff base derivatives showed antioxidant property by two different pathways namely SPLET and HAT mechanisms in DPPH assay. While in ABTS method, the reaction between ABTS radical and Schiff bases involves electron transfer followed by proton transfer (ET-PT) mechanism. The cytotoxicity of these compounds has been evaluated by MTT assay. The results showed that all these compounds are non toxic in nature.

  5. Synthesis, characterization and anti-proliferative activity of heterocyclic hypervalent organoantimony compounds.

    Chen, Yi; Yu, Kun; Tan, Nian-Yuan; Qiu, Ren-Hua; Liu, Wei; Luo, Ning-Lin; Tong, Le; Au, Chak-Tong; Luo, Zi-Qiang; Yin, Shuang-Feng

    2014-05-22

    Three heterocyclic hypervalent organoantimony chlorides RN(CH2C6H4)2SbCl (2a R = t-Bu, 2b R = Cy, 2c R = Ph) and their chalcogenide derivatives [RN(CH2C6H4)2Sb]2O (3a R = t-Bu, 3b R = Cy, 3c R = Ph) were synthesized and characterized by techniques such as (1)H NMR, (13)C NMR, X-ray diffraction, and elemental analysis. It is found that the anti-proliferative activity detected over these compounds can be attributed to the coordination bond between the antimony and nitrogen atoms of these compounds. Moreover, a preliminary study on mechanistic action suggests that the inhibition effect is ascribable to cell cycle arrest and cell apoptosis. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  6. Design, synthesis and evaluation of aromatic heterocyclic derivatives as potent antifungal agents.

    Zhao, Shizhen; Zhang, Xiangqian; Wei, Peng; Su, Xin; Zhao, Liyu; Wu, Mengya; Hao, Chenzhou; Liu, Chunchi; Zhao, Dongmei; Cheng, Maosheng

    2017-09-08

    To further enhance the anti-Aspergillus efficacy of our previously discovered antifungal lead compounds (1), a series of aromatic heterocyclic derivatives were designed, synthesized and evaluated for in vitro antifungal activity. Many of the target compounds showed good inhibitory activity against Candida albicans and Cryptococcus neoformans. In particular, the isoxazole nuclei were more suited for improving the activity against Aspergillus spp. Among these compounds, 2-F substituted analogues 23g and 23h displayed the most remarkable in vitro activity against Candida spp., C. neoformans, A. fumigatus and fluconazole-resistant C.alb. strains, which is superior or comparable to the activity of the reference drugs fluconazole and voriconazole. Notably, the compounds 23g and 23h exhibited low inhibition profiles for various isoforms of human cytochrome P450 and excellent blood plasma stability. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  7. Synthesis and stereochemical investigation of potential saturated heterocyclic drugs Pt. 1

    Bernath, G.

    1982-01-01

    Studies of partially and fully saturated heterocyclic compounds with condensed skeleton containing two heteroatoms are presented. The synthesis, stereochemical and conformation analyses aimed at the synthesis of potential drugs. Dihydro- and tetrahydro-1,3-oxazines were prepared from alicyclic 1,3-amino-alcohols by ring closure with aldehydes or imide esters. 1,3-oxazine-4-one derivatives were prepared by reacting alicyclic cis- and trans-2-hydroxy-1-carboxamides with aliphatic or aromatic aldehides. The conformations of the compounds prepared were determined by means of NMR spectroscopy. The main results of the determination of the steric structure of some representatives of the above described families of compounds by means of X-ray diffraction analysis are also presented. (author)

  8. Heterocyclic Compounds: Effective α-Amylase and α-Glucosidase Inhibitors.

    Saeedi, Mina; Hadjiakhondi, Abbas; Nabavi, Seyed Mohammad; Manayi, Azadeh

    2017-01-01

    Diabetes Mellitus (DM) is a metabolic disease characterized by high blood sugar levels. Recently, it has emerged as an important and global health problem with long-term complications and high economic burden. α-Amylase (α-Amy) and α-glucosidase (α-Gls) are two enzymes which are involved in the hydrolysis of starch into sugars and disaccharides leading to the increase of blood glucose level. Hence, inhibition of α-amylase and α-glucosidase plays key role in the treatment of type 2 diabetes. Heterocyclic compounds -both synthetic and naturally occurring derivatives- possess efficient biological properties. At this juncture, they have demonstrated potent inhibitory activity against α-Amy and α-Gls and were found to be versatile tools for the development of novel anti-diabetic agents.

  9. The role of hydrogen bonding on kinetics of rearrangement of heterocyclic aldoximes in perchloric acide

    Azzouz, A.S.; Abdullah, K.A.; Al-Niemi, I.

    1995-01-01

    Four paris of syn and anti aromatic heterocyclic aldoximes as 2-thiophenealdoxime, 2- furfuraladoxime, 2-pyridinealdoxime and 2-pyrrolealdoxime are prepared. The strcutures of these geometrical isomers are confirmed by the meaasurements of their U.V. I, R and melting points. Experiments show the existence of these aldoximers in an intramolecular hy-drogen bonding with variable strength depending on the hetero ztoms in the aldoximes. The first order rate constants of the rearrangement of syn aldoximes follow the order of hetero S>O>N, while the anti aldoximes show irregular order, Factors governing the aniti constants of the rearrangement of syn and anti aldoximes are analysed. Activation parameters are estimated and discussed on the basis of isokinetic relation-ship. The differences in physical and spectroscpic behavior of aldoximes lead to an important suggestion regarding the configuration of oxime. (author). 27 refs., 2 figs., 2 tabs

  10. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Nitrogen Heterocycles (PANHs)

    Mattioda, A. L.; Hudgins, D. M.; Bauschlicher, C. W.; Allamandola, L. J.; Biemesderfer, C. D.; Rosi, M.

    2002-01-01

    The mid-infrared spectra of the nitrogen-containing heterocyclic polycyclic aromatic compounds 1-azabenz[a]-anthracene; 2-azabenz[a]anthracene; 1-azachrysene; 2-azachrysene; 4-azachrysene; 2-azapyrene, and 7,8 benzoquinoline in their neutral and cation forms were investigated. The spectra of these species isolated in an argon matrix have been measured. Band frequencies and intensities were tabulated and these data compared with spectra computed using density functional theory at the B3LYP level. The overall agreement between experiment and theory is quite good, in keeping with earlier results on homonuclear polycyclic aromatic hydrocarbons. The differences between the spectral properties of nitrogen bearing aromatics and non-substituted, neutral polycyclic aromatic hydrocarbons will be discussed.

  11. Relationship between Antifungal Activity against Candida albicans and Electron Parameters of Selected N-Heterocyclic Thioamides

    Stachowicz, Jadwiga; Krajewska-Kułak, Elżbieta; Łukaszuk, Cecylia; Niewiadomy, A.

    2014-01-01

    Due to the increasing demand for new pharmaceuticals showing biological activity against pathogenic microorganisms, there is increasing search for new compounds with predicted biological activity. Variously substituted thioamide derivatives with 1.3 and 1.2 ring of thiazole and 1,3,4-thiadiazole, as well as pyrazole were assessed for their activity against Candida albicans. Activity of majority of tested thioamides was larger as compared with that of the reference drugs. The electron parameters of obtained N-heterocyclic thioamides were determined and dependencies on their biological activity against Candida albicans were studied. The best electron compliance of produced bindings with the activity against Candida albicans was observed for the derivatives containing 1,3,4-thiadiazole ring. PMID:25284926

  12. Antidepressant potential of nitrogen-containing heterocyclic moieties: An updated review

    Nadeem Siddiqui

    2011-01-01

    Full Text Available Depression is currently the fourth leading cause of disease or disability worldwide. Antidepressant is approved for the treatment of major depression (including paediatric depression, obsessive-compulsive disorder (in both adult and paediatric populations, bulimia nervosa, panic disorder and premenstrual dysphoric disorder. Antidepressant is a psychiatric medication used to alleviate mood disorders, such as major depression and dysthymia and anxiety disorders such as social anxiety disorder. Many drugs produce an antidepressant effect, but restrictions on their use have caused controversy and off-label prescription a risk, despite claims of superior efficacy. Our current understanding of its pathogenesis is limited and existing treatments are inadequate, providing relief to only a subset of people suffering from depression. Reviews of literature suggest that heterocyclic moieties and their derivatives has proven success in treating depression.

  13. EVALUATION OF THE ANTIMICROBIAL EFFECTS OF NEW HETEROCYCLIC BIS-QUATERNARY AMMONIUM COMPOUNDS ON BIOFILMS

    OANA E. CONSTANTIN

    2016-07-01

    Full Text Available Considering the well-known mechanism of adaptable resistance of microorganisms to chemical compounds through biofilms formation and the widespread use of N-heterocyclic quaternary ammonium salts (QAC as disinfectants, in this study we have evaluate the effect of 8 newly synthesized symmetrical and unsymmetrical diquaternary ammonium salts of 1,2-bis-(4-pyridil-ethane on bacterial biofilms produced by three different bacterial strains. The effect of the exposure to quaternary ammonium salts on biofilm communities was investigated within biofilms obtained in a conventional testing system, on stainless steel and glass surfaces. Differential plate counts were used to characterize the developed communities and the effects of QAC exposure and the results were correlated with epifluorescence microphotographs. The data obtained revealed a significant reduction of bacterial cells in the biofilms tested with 4-7 log CFU for all the QAC.

  14. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

    Zong Guan

    2014-04-01

    Full Text Available Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes which can be trapped as rhodium complexes (X-ray analysis. In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole–indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole–indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis. Results of DFT calculations are presented.

  15. Amide Synthesis from Alcohols and Amines Catalyzed by Ruthenium N-Heterocyclic Carbene Complexes

    Dam, Johan Hygum; Osztrovszky, Gyorgyi; Nordstrøm, Lars Ulrik Rubæk

    2010-01-01

    The direct synthesis of amides from alcohols and amines is described with the simultaneous liberation of dihydrogen. The reaction does not require any stoichiometric additives or hydrogen acceptors and is catalyzed by ruthenium N-heterocyclic carbene complexes. Three different catalyst systems...... are presented that all employ 1,3-diisopropylimidazol-2-ylidene (IiPr) as the carbene ligand. In addition, potassium tert-butoxide and a tricycloalkylphosphine are required for the amidation to proceed. In the first system, the active catalyst is generated in situ from [RuCl2(cod)] (cod = 1,5-cyclooctadiene), 1...... chloride and base. A range of different primary alcohols and amines have been coupled in the presence of the three catalyst systems to afford the corresponding amides in moderate to excellent yields. The best results are obtained with sterically unhindered alcohols and amines. The three catalyst systems do...

  16. New Homologues Series of Heterocyclic Schiff Base Ester: Synthesis and Characterization

    Yee-Ting Chong

    2016-01-01

    Full Text Available A homologous series of liquid crystal bearing with heterocyclic thiophene Schiff base ester with alkanoyloxy chain (CH3(CH2nCOO–, where n=4, 6, 8, 10, 12, 14, 16 was successfully synthesized through the modification of some reported methods. The structural information of these compounds was isolated and characterized through some spectroscopic techniques, such as FTIR, 1H, and 13C NMR and elemental analysis. Textural observation was carried out using a polarizing optical microscope (POM over heating and cooling cycles. It was found that all synthesized compounds (3a–g exhibited an enantiotropic nematic phase upon the heating and cooling cycle with high thermal stability. Moreover, a characteristic bar transition texture was observed for compounds 3f and 3g which have shown transition of nematic-to-smectic C phase. This has been further confirmed by obtaining relative phase transition temperature using the differential scanning calorimetry (DSC.

  17. Acrolein contributes strongly to antimicrobial and heterocyclic amine transformation activities of reuterin.

    Engels, Christina; Schwab, Clarissa; Zhang, Jianbo; Stevens, Marc J A; Bieri, Corinne; Ebert, Marc-Olivier; McNeill, Kristopher; Sturla, Shana J; Lacroix, Christophe

    2016-11-07

    Glycerol/diol dehydratases catalyze the conversion of glycerol to 3-hydroxypropionaldehyde (3-HPA), the basis of a multi-component system called reuterin. Reuterin has antimicrobial properties and undergoes chemical conjugation with dietary heterocyclic amines (HCAs). In aqueous solution reuterin is in dynamic equilibrium with the toxicant acrolein. It was the aim of this study to investigate the extent of acrolein formation at various physiological conditions and to determine its role in biological and chemical activities. The application of a combined novel analytical approach including IC-PAD, LC-MS and NMR together with specific acrolein scavengers suggested for the first time that acrolein, and not 3-HPA, is the active compound responsible for HCA conjugation and antimicrobial activity attributed to reuterin. As formation of the HCA conjugate was observed in vivo, our results imply that acrolein is formed in the human gut with implications on detoxification of HCAs. We propose to re-define the term reuterin to include acrolein.

  18. Tuning and Quantifying Steric and Electronic Effects of N-Heterocyclic Carbenes

    Falivene, Laura

    2014-07-12

    This chapter states that the main handles for tuning steric and electronic effects are the substituents on N atoms, the nature of the C4-C5 bridge (either saturated or unsaturated), and the substituents on the C4 and C5 atoms. The initial intuition that steric properties of N-heterocyclic carbenes (NHCs) could be modulated and could impact catalytic behavior stimulated the development of steric descriptors to quantify the steric requirement of different NHCs and, possibly, to compare them with tertiary phosphines. NHCs can be classified as typically strong σ-basic/π-acid ligands, although they have been also shown to exhibit reasonable π-basic properties. This electronic modularity allows NHC ligands to adapt flexibly to different chemical environments represented by a transition metal and the other ligands. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.

  19. Authenticity analysis of citrus essential oils by HPLC-UV-MS on oxygenated heterocyclic components

    Hao Fan

    2015-03-01

    Full Text Available Citrus essential oils are widely applied in food industry as the backbone of citrus flavors. Unfortunately, due to relatively simple chemical composition and tremendous price differences among citrus species, adulteration has been plaguing the industry since its inception. Skilled blenders are capable of making blends that are almost indistinguishable from authentic oils through conventional gas chromatography analysis. A reversed-phase high performance liquid chromatography (HPLC method was developed for compositional study of nonvolatile constituents in essential oils from major citrus species. The nonvolatile oxygenated heterocyclic components identified in citrus oils were proved to be more effective as markers in adulteration detection than the volatile components. Authors are hoping such an analysis procedure can be served as a routine quality control test for authenticity evaluation in citrus essential oils.

  20. Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

    Wendlandt, Alison E; Stahl, Shannon S

    2014-01-08

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts.

  1. Trinitromethyl Heterocyclic Oxidizers as a Solid Propellant Ingredient Final Report CRADA No TC02146.0

    Pagoria, P. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Racoveanu, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2017-08-15

    This was a collaborative effort between Lawrence Livermore National Security, LLC as manager and operator of Lawrence Livermore National Laboratory (LLNL) and Physical Sciences, Inc. (PSI), to develop a synthesis of two novel energetic heterocyclic oxidizers as possible replacements for ammonium perchlorate (AP) in rocket propellant formulations. This CRADA resulted from the award of the Phase I Small Business Technology Transfer (STTR) from DOD. The CRADA consisted of two phases. The goal for Phase 1 was to produce a new oxidizer called TNMDNP. Phase 2 is optional (based on the success of Phase 1) and the goal of Phase 2 (optional) was to produce a new oxidizer called TNMDNT. Phase 2 tasks would be performed based on the successful results of Phase 1.

  2. N-heterocyclic carbene metal complexes as bio-organometallic antimicrobial and anticancer drugs.

    Patil, Siddappa A; Patil, Shivaputra A; Patil, Renukadevi; Keri, Rangappa S; Budagumpi, Srinivasa; Balakrishna, Geetha R; Tacke, Matthias

    2015-01-01

    Late transition metal complexes that bear N-heterocyclic carbene (NHC) ligands have seen a speedy growth in their use as both, metal-based drug candidates and potentially active homogeneous catalysts in a plethora of C-C and C-N bond forming reactions. This review article focuses on the recent developments and advances in preparation and characterization of NHC-metal complexes (metal: silver, gold, copper, palladium, nickel and ruthenium) and their biomedical applications. Their design, syntheses and characterization have been reviewed and correlated to their antimicrobial and anticancer efficacies. All these initial discoveries help validate the great potential of NHC-metal derivatives as a class of effective antimicrobial and anticancer agents.

  3. Structural Correlation of Some Heterocyclic Chalcone Analogues and Evaluation of Their Antioxidant Potential

    Hoong-Kun Fun

    2013-09-01

    Full Text Available A series of six novel heterocyclic chalcone analogues 4(a–f has been synthesized by condensing 2-acetyl-5-chlorothiophene with benzaldehyde derivatives in methanol at room temperature using a catalytic amount of sodium hydroxide. The newly synthesized compounds are characterized by IR, mass spectra, elemental analysis and melting point. Subsequently; the structures of these compounds were determined using single crystal X-ray diffraction. All the synthesized compounds were screened for their antioxidant potential by employing various in vitro models such as DPPH free radical scavenging assay, ABTS radical scavenging assay, ferric reducing antioxidant power and cupric ion reducing antioxidant capacity. Results reflect the structural impact on the antioxidant ability of the compounds. The IC50 values illustrate the mild to good antioxidant activities of the reported compounds. Among them, 4f with a p-methoxy substituent was found to be more potent as antioxidant agent.

  4. Sur: uma minoria cosmopolita na periferia ocidental Sur: a cosmopolitan minority on the western periphery

    Maria Teresa Gramuglio

    2007-06-01

    Full Text Available Este artigo explora as condições e as disposições que tornaram possível o surgimento da revista Sur e a formação do grupo cultural de mesmo nome. Propõe critérios para uma periodização que leve em conta, junto com os indícios materiais, as circunstâncias históricas e culturais cambiantes pelas quais a publicação passou durante sua longa vida (1931-1991. Assinala alguns dos principias temas ideológicos e estéticos que foram abordados em suas páginas. Caracteriza o projeto inicial e as transformações imprimidas pela vontade de sua diretora, Victoria Ocampo, e as mudanças nas relações e problemáticas do campo intelectual.This article explores the conditions and dispositions that enabled the emergence of the magazine Sur and the formation of the cultural group of the same name. It sets out the criteria for a periodization that takes into account, along with material factors, the shifting historical and cultural circumstances experienced by the publication over its 60-year life-span (1931-1991. The text highlights some of the main ideological and aesthetic themes to have filled the magazine's pages. It describes the original project and the transformations introduced by its chief editor, Victoria Ocampo, as well as the changes in the relations and problematics of the intellectual field.

  5. Más allá de los mitos: análisis de la Cooperación Sur-Sur y Norte-Sur en el Ecuador. Sector Educación, período 2003- 2008

    Escobar Sánchez, Wladimir Alexander

    2012-01-01

    La presente tesis de maestría analiza a la cooperación Norte-Sur y Sur-Sur como los dos principales modelos de funcionamiento de la cooperación hoy en día, a través de dos programas de ayuda internacional en el sector educación, en el período 2003-2008. El uno referente a la cooperación Norte-Sur, y el otro a la cooperación Sur-Sur. El propósito que presenta este trabajo académico es explicar a la cooperación internacional al desarrollo tomando en consideración a la teoría real...

  6. Generation of N-Heterocycles via Tandem Reactions of N '-(2-Alkynylbenzylidene)hydrazides.

    Qiu, Guanyinsheng; Wu, Jie

    2016-02-01

    As a powerful synthon, N '-(2-alkynylbenzylidene)hydrazides have been utilized efficiently for the construction of N-heterocycles. Since N '-(2-alkynylbenzylidene)hydrazides can easily undergo intramolecular 6-endo cyclization promoted by silver triflate or electrophiles, the resulting isoquinolinium-2-yl amides can proceed through subsequent transformations including [3 + 2] cycloaddition, nucleophilic addition, and [3 + 3] cycloaddition. Several unexpected rearrangements via radical processes were observed in some cases, which afforded nitrogen-containing heterocycles with molecular complexity. Reactive partners including internal alkynes, arynes, ketenimines, ketenes, allenoates, and activated alkenes reacted through [3 + 2] cycloaddition and subsequent aromatization, leading to diverse H-pyrazolo[5,1-a]isoquinolines with high efficiency. Nucleophilic addition to the in situ generated isoquinolinium-2-yl amide followed by aromatization also produced H-pyrazolo[5,1-a]isoquinoline derivatives when terminal alkynes, carbonyls, enamines, and activated methylene compounds were used as nucleophiles. Isoquinoline derivatives were obtained when indoles or phosphites were employed as nucleophiles in the reactions of N '-(2-alkynylbenzylidene)hydrazides. A tandem 6-endo cyclization and [3 + 3] cycloaddition of cyclopropane-1,1-dicarboxylates with N '-(2-alkynylbenzylidene)hydrazides was observed as well. Small libraries of these compounds were constructed. Biological evaluation suggested that some compounds showed promising activities for inhibition of CDC25B, TC-PTP, HCT-116, and PTP1B. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Hausse des taxes sur le tabac et politiques de lutte antitabac au ...

    Par ailleurs, les études existantes sur les effets des taxes sur le tabac sont fondées sur l'" élasticité de la demande en fonction du prix ", une mesure qui indique l'évolution de la demande globale de cigarettes en réaction à une modification des prix, mais qui ne tient pas compte des effets d'une augmentation des taxes sur ...

  8. Rapport annuel au Parlement Loi sur la protection des ...

    Larocque, Samia

    1 juil. 1983 ... TBS/SCT 350-63 (Rév. 2011/03). 31/03/2014. 01/04/2013. Période visée par le rapport : Reçues pendant la période visée par le rapport. Total. En suspens à la fin de la période de rapport précédente. Rapport statistique sur la Loi sur la protection des renseignements personnels. Nom de l'institution :.

  9. Commission des Nations Unies sur les produits indispensables aux ...

    Étude des soins de santé primaires dispensés dans les pays du cône Sud. Les pays membres du Réseau de recherche sur les systèmes et services de santé dans les pays du cône Sud (Red de Investigación en Sistemas y Servicios de Salud en el Cono Sur) ont des systèmes de... Voir davantageÉtude des soins de santé ...

  10. Droits, justice et réseaux sociaux sur Internet (Amérique latine ...

    ... sur la question de la protection des renseignements personnels sur Internet, ... Derechos y justicia y el movimiento social en internet (5 de agosto de 2009 ... Programme de recherche sur le virus Zika Canada-Amérique latine et Caraïbes.

  11. Hausse des taxes sur le tabac dans trois pays d'Amérique centrale ...

    Les chercheurs mèneront des études sur la demande de produits du tabac dans le ... sur les techniques modernes de contrôle de la chaîne d'approvisionnement, ... IWRA/CRDI sur les changements climatiques et la gestion adaptive de l'eau.

  12. Les mesures de gel et de confiscation en vertu de la Loi sur les embargos

    Schnyder, Nicolas

    2009-01-01

    Etude du mécanisme d'adoption des mesures de gel et de confiscation en vertu de la Loi sur les embargos et leurs conséquences tant sur la personne principalement touchée par ces mesures que sur les tiers.

  13. Données préliminaires sur le paludisme humain en zones rurale et ...

    SARAH

    31 juil. 2017 ... axée sur le diagnostic précoce et la prise en charge rapide des ... recherche investigue sur les connaissances, attitudes et ... paludisme et (vi) sur la source de traitement du paludisme. ... technique ELISA (Burkot et al., 1984).

  14. Effet de la composition de différents substrats culturaux sur ...

    SARAH

    31 janv. 2014 ... Effet de la substrats culturaux sur paramètres de croissance ... des graines, mais ce substrat a donné des performances acceptables sur la croissance longitudinale des ..... élevés en conteneurs sur différents types de.

  15. Sur terre comme sur mer: organisations spatiales en mer du Nord et mer de Norvège

    Maryvonne LE BERRE

    1998-09-01

    Full Text Available L'article montre, au moyen de représentations cartographiques et graphiques, les structures spatiales développées en mer pour l'exploitation des hydrocarbures. Malgré les différences de milieu, l'appropriation et l'occupation territoriales du domaine maritime s'effectuent selon les mêmes principes que sur le continent, à ceci près que ce qui s'étale en surface sur le continent se développe à la verticale en mer.

  16. La cooperación Sur-Sur agrícola argentina con África Subsahariana: una historia que comienza

    Morasso, Carla

    2015-01-01

    [es] En la última década Argentina ha sido un actor dinámico de la cooperación Sur-Sur. Sus acciones se han dirigido principalmente hacia América Latina, pero también se han promovido los vínculos con Asia y África. El artículo analiza particularmente la cooperación Sur-Sur entre Argentina y países de África Subsahariana en materia de desarrollo agrícola en el período 2003-2013, donde se destacan los roles del Fondo Argentino de Cooperación Sur-Sur y Triangula...

  17. Conférence sur l'efficacité

    Jullien, François

    2005-01-01

    Philosophe et sinologue, François Jullien présente ici une conférence qu'il a prononcée auprès de chefs d'entreprise et dans le milieu du management. D'un côté, la conception européenne de l'efficacité est liée à la modélisation comme à la finalité et revendique l'action jusqu'à l'héroïsme ; de l'autre, la pensée chinoise de l'efficience, indirecte et discrète, s'appuie sur le potentiel de situation et induit des " transformations silencieuses ", sans éclat ni même événement. Par-delà cet écart, il s'agira d'interroger la nature de l'effectivité ; ou comment l'intervention humaine réussit à se brancher sur la propension des choses et s'y laisse intégrer. Ce propos se garde donc de séparer tant soit peu l'art d'opérer sur des situations et l'exercice de la philosophie ; en résultent des effets de lecture portant sur l'histoire du XXe siècle ainsi que la géopolitique - et géoéthique - à venir.

  18. Connaissances et attitudes des manipulateurs radio du Togo sur l ...

    Objectif : Evaluer les connaissances et les attitudes des manipulateurs togolais sur l'irradiation médicale des grossesses. Matériels et Méthode : Etude transversale menée en Avril 2011 chez 72 manipulateurs de radiologie des structures sanitaires publiques et privées du Togo. Résultats : Le quart des manipulateurs ...

  19. Sur?Surva - the Forgotten God [In Bulgarian

    G. Simeonova

    2014-12-01

    Full Text Available Тhis paper deals with the neglected god – Sur/Surva. The author considers in full detail this problem, finding an evidence for the statements proposed by a new perusal of Stefan Verkovich’s Veda Slovena.

  20. Suivi sur le programme de mentorat de journalistes scientifiques des ...

    12 oct. 2010 ... Godefroy Chabi, un jeune journaliste scientifique, se présente à l'accueil d'un ... Il doit rédiger un article sur l'éducation et les droits de l'homme. ... et de Agence suédoise de coopération internationale au développement.

  1. La croissance demographique et son impact sur le developpement ...

    La croissance demographique et son impact sur le developpement des grandes villes au ... La ville de Porto-Novo au Bénin n'est pas en marge de cette réalité que ... and the need for improving its framework of life through its development.

  2. Soutien institutionnel à des organismes de recherche sur les ...

    Asie du Sud (le Bangladesh, l'Inde, le Népal, le Pakistan et le Sri Lanka). Parmi les 16 demandeurs d'Asie du Sud retenus, neuf viennent de l'Inde. La recherche sur les politiques en Asie du Sud s'effectue principalement en Inde, forte d'une ...

  3. Professorat de recherche sur les droits de la personne reconnus ...

    Pour ce projet, le CRDI s'associe à la Norman Paterson School of International Affairs (NPSIA) pour réaliser un programme de recherche portant sur les droits de la personne reconnus internationalement. La subvention servira à payer pendant deux ans la moitié du salaire et des avantages sociaux du professeur agrégé ...

  4. International Development Research Centre Act Loi sur le Centre de ...

    1 juin 2009 ... research includes any scientific or technical inquiry or experimentation that is .... data centres and facilities for research and other activ- ities;. (b) initiate and ..... Loi sur la pension de la fonction publique ne s'applique pas aux ...

  5. L'IMPACT DES DEPENSES D'INFRASTRUCTURES SUR LA ...

    Administrateur

    l'économétrie, dans l'analyse de l'impact des dépenses d'infras- tructures sur la .... montre que les politiques budgétaires de relance peuvent avoir un impact à long terme ...... Sciences Economiques et Sciences de Gestion Université d'Alger.

  6. Renforcement de la recherche sur les politiques et du plaidoyer ...

    Nouveau webinaire IWRA/CRDI sur les changements climatiques et la gestion adaptive de l'eau. L'Association internationale de ressources en eau (IWRA), en étroite collaboration avec le CRDI, organise un webinaire intitulé "Changements climatiques et gestion adaptive de l'eau: des... Voir davantageNouveau webinaire ...

  7. Influence du chlorpyriphos-ethyl sur quelques paramtres de ...

    admin

    testicules, les caractéristiques des spermatozoïdes épididymaires et sur les performances de reproduction ont été étudiés. .... par le test d'ANOVA et séparés par le test de. Duncan au ..... Dunnick JK, Gupta BN, Harris MW, Lamb. JC. 1984.

  8. Reactivity of N-heterocyclic carbene-pyridine palladacyclopentadiene complexes toward halogen addition. The unpredictable course of the reaction.

    Visentin, Fabiano; Santo, Claudio; Scattolin, Thomas; Demitri, Nicola; Canovese, Luciano

    2017-08-08

    As an extension of a previously published work we have reacted some palladacyclopentadiene complexes stabilized by bidentate N-heterocyclic carbene-pyridine or monodentate N-heterocyclic carbene-pyridine and isocyanide ligands with the halogens I 2 and Br 2 . All the bidentate and monodentate complexes react with halogens to give at first the expected σ-coordinated butadienyl fragment. However, two of the less hindered NHC carbene-pyridine bidentate butadienyl iodo derivatives undergo a further rearrangement and novel Pd(ii) complexes characterized by a ten term coordinative ring were isolated and characterized. In the most favorable case we were able to carry out the kinetics of rearrangement and measure its reaction rate. Moreover, we have surmised a plausible mechanism on the basis of a dedicated computational approach and in one case the surprising structure characterized by the ten term coordinative ring was resolved by X-ray diffraction.

  9. Amino substituted nitrogen heterocycle ureas as kinase insert domain containing receptor (KDR inhibitors: Performance of structure–activity relationship approaches

    Hayriye Yilmaz

    2015-06-01

    Full Text Available A quantitative structure–activity relationship (QSAR study was performed on a set of amino-substituted nitrogen heterocyclic urea derivatives. Two novel approaches were applied: (1 the simplified molecular input-line entry systems (SMILES based optimal descriptors approach; and (2 the fragment-based simplex representation of molecular structure (SiRMS approach. Comparison with the classic scheme of building up the model and balance of correlation (BC for optimal descriptors approach shows that the BC scheme provides more robust predictions than the classic scheme for the considered pIC50 of the heterocyclic urea derivatives. Comparison of the SMILES-based optimal descriptors and SiRMS approaches has confirmed good performance of both techniques in prediction of kinase insert domain containing receptor (KDR inhibitory activity, expressed as a logarithm of inhibitory concentration (pIC50 of studied compounds.

  10. Multicomponent synthesis of unsymmetrical unsaturated N-heterocyclic carbene precursors and their related transition-metal complexes

    Queval, Pierre

    2013-12-04

    A low-cost, modular, and easily scalable multicomponent procedure affording access in good yields and excellent selectivity (up to 93 %) to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl-imidazolium salts is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron donor ability, high steric discrimination, and modular steric demand. A low-cost, modular, and easily scalable multicomponent procedure, affording access to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl- imidazolium salts in good yields and excellent selectivities, is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron-donor ability, high steric discrimination, and modular steric demand. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Single-catalyst high-weight% hydrogen storage in an N-heterocycle synthesized from lignin hydrogenolysis products and ammonia.

    Forberg, Daniel; Schwob, Tobias; Zaheer, Muhammad; Friedrich, Martin; Miyajima, Nobuyoshi; Kempe, Rhett

    2016-10-20

    Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this, compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein, we report that catalytically modified lignin, an indigestible, abundantly available and hitherto barely used biomass, can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed, which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore, a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia, and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage.

  12. The formation of electronically excited fragments by the electron impact of furan and related five-membered heterocycles

    Tokue, Ikuo; Ikarashi, Masami; Takizawa, Sadachika; Ito, Yoshio

    1983-01-01

    In the wavelength region of 200-600 nm, photoemissions from electronically excited H, CH, C 2 , and CS (only from thiophene and tetrahydrothiophene) were observed when furan, tetrahydrofuran, thiophene, and tetrahydrothiophene were excited by electron impact (0-70 eV). Hydrogen atoms (n = 4) and CH(A 2 Δ) radicals were produced from these five-membered heterocycles via single collision excitations, while CS(A 1 PI) radicals from thiophene and tetrahydrothiophene were partly formed in secondary processes. The appearance potentials for the hydrogen Balmer β and the CH(A 2 Δ-X 2 PI) bands from these five-membered heterocycles are determined, and the dissociation processes forming H(n = 4) and CH(A) are discussed. (author)

  13. Assembly of Four Diverse Heterocyclic Libraries Enabled by Prins Cyclization, Au-Catalyzed Enyne Cycloisomerization, and Automated Amide Synthesis

    Cui, Jiayue; Chai, David I.; Miller, Christopher; Hao, Jason; Thomas, Christopher; Wang, JingQi; Scheidt, Karl A.; Kozmin, Sergey A.

    2013-01-01

    We describe a unified synthetic strategy for efficient assembly of four new heterocyclic libraries. The synthesis began by creating a range of structurally diverse pyrrolidinones or piperidinones. Such compounds were obtained in a simple one-flask operation starting with readily available amines, ketoesters, and unsaturated anhydrides. The use of tetrahydropyran-containing ketoesters, which were rapidly assembled by our Prins cyclization protocol, enabled efficient fusion of pyran and piperidinone cores. A newly developed Au(I)-catalyzed cycloisomerization of alkyne-containing enamides further expanded heterocyclic diversity by providing rapid entry into a wide range of bicyclic and tricyclic dienamides. The final stage of the process entailed diversification of each of the initially produced carboxylic acids using a fully automated platform for amide synthesis, which delivered 1872 compounds in high diastereomeric and chemical purity. PMID:22860634

  14. Positron annihilation lifetime studies of changes in free volume on some biorelevant nitrogen heterocyclic compounds and their S-glycosylation

    Mahmoud, K.R.; Khodair, A.I.; Shaban, S.Y.

    2015-01-01

    A series of N-heterocyclic compounds was investigated by positron annihilation lifetime spectroscopy as well as Doppler broadening of annihilation radiation (DBAR) at room temperature. The results showed that the formation probability and life time of ortho-positronium in this series are structure and electron-donation character dependent, and can give more information about the structure. The DBAR provides direct information about the change of core and valance electrons as well as the number of defect types present in these compounds. - Highlights: • N-heterocyclic compounds were studied by PALS and DBAR at room temperature. • These compounds contain thiohydantoins which have wide applications as anticarcinogenic, antiviral, human immunodeficiency virus (HIV) and antimicrobial activity. • The DBAR provides direct information about the change of core and valance electrons as well as the number of defect types present in these compounds.

  15. An electrochemical procedure coupled with a Schiff base method; application to electroorganic synthesis of new nitrogen-containing heterocycles

    Dowlati, Bahram; Othman, Mohamed Rozali

    2013-01-01

    The synthesis of Nitrogen-containing heterocycles has been achieved using chemical and electrochemical methods, respectively. The direct chemical synthesis of nucleophiles proceeds through the Schiff base chemical reaction. This procedure offers an alternate reaction between dicarbonyl compounds and diamines leads to the formation of products. The results indicate that the Schiff base chemical method for synthesis of the product has successfully performed in excellent overall yield. In the electrochemical step, a series of Nitrogen-containing compounds were electrosynthesized. Various parameters such as the applied potential, pH of the electrolytic solution, cell configuration and also purification techniques, were carried out to optimize the yields of corresponding products. New Nitrogen-containing heterocycle derivatives were synthesized using an electrochemical procedure coupled with a Schiff base as a facile, efficient and practical method. The products have been characterized after purification by IR, 1 H NMR, 13 C NMR and ESI-MS 2

  16. Synthesis and Biological Evaluation of Novel Benzimidazole Derivatives Bearing a Heterocyclic Ring at 4/5 Position

    Wubulikasimu, Reyila; Yang, Yanbing; Xue, Fei; Luo, Xianjin; Shao, Dongping; Li, Yuhuan; Gao, Rongmei; Ye, Weidong

    2013-01-01

    A series of novel benzimidazole derivatives bearing a heterocyclic ring as oxadiazole (21-32), thiadiazole (33-34), triazole (35-36) were synthesized and evaluated for their activities against Coxsackie virus B3 and B6 in Vero cells. Compounds 21-26, 31-36 with moieties of 2'-pyridyl, 3'-pyridyl and 4'-pyridyl at the 2-position and oxadiazoles, thiadiazole, or triazole substituent at the 4- or 5-position generally displayed activities against CVB3 and CVB6. Especially compound 24 (IC 50 = 1.08 μg/mL, SI = 61.7 against CVB3) was the promising candidate as lead compound for anti-enteroviral drug. It was observed in the incorporation of heterocyclic rings in benzimidazole at the 5-position could enhance their biological activities

  17. N-Heterocyclic Carbene-Catalyzed Vinylogous Mukaiyama Aldol Reaction of α-Keto Esters and α-Trifluoromethyl Ketones

    Du, Guang-Fen; Wang, Ying; Xing, Fen; Xue, Mei; Guo, Xu-Hong; Huang, Kuo-Wei; Dai, Bin

    2015-01-01

    © Georg Thieme Verlag Stuttgart · New York · Synthesis 2016. N-Heterocyclic carbene (NHC)-catalyzed vinylogous Mukaiyama aldol reaction of ketones was developed. Under the catalysis of 5 mol% NHC, α-keto esters and α-trifluoromethyl ketones reacted with 2-(trimethysilyloxy)furan efficiently to produce γ-substituted butenolides containing adjacent quaternary and tertiary carbon centers in high yields with good diastereoselectivities.

  18. Build/Couple/Pair and Multifunctional Catalysis Strategies for the Synthesis of Heterocycles from Simple Starting Materials

    Ascic, Erhad

    . Multifunctional Catalysis: Synthesis of Heterocycles from Simple Starting Materials A multifunctional catalysis approach, involving a ruthenium-catalyzed tandem ringclosing metathesis/isomerization/N-acyliminium cyclization sequence, is described. Double bonds created during ring-closing metathesis isomerize......, a series of interesting indolizidinones are formed in good yields with excellent diastereoselectivities, including a formal total synthesis of the antiparasitic natural product harmicine and the first total synthesis of mescalotam. Furthermore, preliminary asymmetric variants of the tandem process have...

  19. Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

    Manzini, Simone

    2015-03-01

    The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

  20. Stereochemical Basis for a Unified Structure Activity Theory of Aromatic and Heterocyclic Rings in Selected Opioids and Opioid Peptides

    Joel S. Goldberg

    2010-02-01

    Full Text Available This paper presents a novel unified theory of the structure activity relationship of opioids and opioid peptides. It is hypothesized that a virtual or known heterocyclic ring exists in all opioids which have activity in humans, and this ring occupies relative to the aromatic ring of the drug, approximately the same plane in space as the piperidine ring of morphine. Since the rings of morphine are rigid, and the aromatic and piperidine rings are critical structural components for morphine’s analgesic properties, the rigid morphine molecule allows for approximations of the aromatic and heterocyclic relationships in subsequent drug models where bond rotations are common. This hypothesis and five propositions are supported by stereochemistry and experimental observations. Proposition #1 The structure of morphine provides a template. Proposition #2 Steric hindrance of some centric portion of the piperidine ring explains antagonist properties of naloxone, naltrexone and alvimopam. Proposition #3 Methadone has an active conformation which contains a virtual heterocyclic ring which explains its analgesic activity and racemic properties. Proposition #4 The piperidine ring of fentanyl can assume the morphine position under conditions of nitrogen inversion. Proposition #5 The first 3 amino acid sequences of beta endorphin (l-try-gly-gly and the active opioid dipeptide, l-tyr-pro, (as a result of a peptide turn and zwitterion bonding form a virtual piperazine-like ring which is similar in size, shape and location to the heterocyclic rings of morphine, meperidine, and methadone. Potential flaws in this theory are discussed. This theory could be important for future analgesic drug design.

  1. Alkyne-Azide Cycloaddition Catalyzed by Silver Chloride and “Abnormal” Silver N-Heterocyclic Carbene Complex

    Aldo I. Ortega-Arizmendi

    2013-01-01

    Full Text Available A library of 1,2,3-triazoles was synthesized from diverse alkynes and azides using catalytic amounts of silver chloride instead of copper compounds. In addition, a novel “abnormal” silver N-heterocyclic carbene complex was tested as catalyst in this process. The results suggest that the reaction requires only 0.5% of silver complex, affording 1,2,3-triazoles in good yields.

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

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

    2014-12-01

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

  3. Cyclometalated N-heterocyclic carbene iridium(iii) complexes with naphthalimide chromophores: a novel class of phosphorescent heteroleptic compounds.

    Lanoë, Pierre-Henri; Chan, Jonny; Groué, Antoine; Gontard, Geoffrey; Jutand, Anny; Rager, Marie-Noelle; Armaroli, Nicola; Monti, Filippo; Barbieri, Andrea; Amouri, Hani

    2018-03-06

    A series of cyclometalated N-heterocyclic carbene complexes of the general formula [Ir(C^N) 2 (C^C:)] has been prepared. Two sets of compounds were designed, those where (C^C:) represents a bidentate naphthalimide-substituted imidazolylidene ligand and (C^N) = ppy (3a), F2ppy (4a), bzq (5a) and those where (C^C:) represents a naphthalimide-substituted benzimidazolylidene ligand and (C^N) = ppy (3b), F2ppy (4b), bzq (5b). The naphthalimide-imidazole and naphthalimide-benzimidazole ligands 1a,b and the related imidazolium and benzimidazolium salts 2a,b were also prepared and fully characterized. The N-heterocyclic carbene Ir(iii) complexes have been characterized by NMR spectroscopy, cyclic voltammetry and elemental analysis. Moreover, the molecular structures of one imidazolium salt and four Ir(iii) complexes were determined by single-crystal X-ray diffraction. The structures provide us with valuable information, most notably the orientation of the naphthalimide chromophore with respect to the N-heterocyclic carbene moiety. All compounds are luminescent at room temperature and in a frozen solvent at 77 K, exhibiting a broad emission band that extends beyond 700 nm. The presence of the naphthalimide moiety changes the character of the lowest excited state from 3 MLCT to 3 LC, as corroborated by DFT and TD-DFT calculations. Remarkably, replacing imidazole with a benzimidazole unit improves the quantum yields of these compounds by decreasing the k nr values which is an important feature for optimized emission performance. These studies provide valuable insights about a novel class of N-heterocyclic carbene-based luminescent complexes containing organic chromophores and affording metal complexes emitting across the red-NIR range.

  4. Petroleum geochemistry of the Potwar Basin, Pakistan: II – Oil classification based on heterocyclic and polycyclic aromatic hydrocarbons

    Asif, Muhammad; Fazeelat, Tahira

    2012-01-01

    In a previous study, oils in the Potwar Basin (Upper Indus) of Pakistan were correlated based on the dissimilarity of source and depositional environment of organic matter (OM) using biomarkers and bulk stable isotopes. This study is aimed at supporting the classification of Potwar Basin oils into three groups (A, B and C) using the distribution of alkylnaphthalenes, alkylphenanthrenes, alkyldibenzothiophenes, alkyldibenzofurans, alkylfluorenes, alkylbiphenyls, triaromatic steroids, methyl triaromatic steroids, retene, methyl retenes and cadalene. The higher relative abundance of specific methyl isomers of naphthalene and phenanthrene and the presence of diagnostic aromatic biomarkers clearly indicate the terrigenous and oxic depositional environment of OM for group A oil. Group B and C oils are of marine origin and the aforementioned heterocyclic and polycyclic aromatic hydrocarbons (HCs) differentiate them clearly into two different groups. The relative percentages of heterocyclic aromatic HCs reveal that the distribution of these compounds is controlled by the depositional environment of the OM. Sulfur-containing heterocyclic aromatic HCs are higher in crude oils generated from source rocks deposited in suboxic depositional environments, while oxygen-containing heterocyclic aromatic HCs in combination with alkylfluorenes are higher in marine oxic and deltaic oils. Biomarker and aromatic HC parameters do not indicate significant differences in the thermal maturity of Potwar Basin oils. Triaromatic and methyl triaromatic steroids support the division of Potwar Basin oils into the three groups and their relative abundances are related to source OM rather than thermal maturity. Significantly higher amounts of C 20 and C 21 triaromtic steroids and the presence or absence of long chain triaromatic steroids (C 25 , C 26 , C 27 , and C 28 ) indicates that these compounds are probably formed from different biological precursors in each group. Different isomers of methyl

  5. Synthesis and antibacterial activity of novel Pyrazolo [3, 4-B] quinoline based heterocyclic azo compounds and their dyeing performance

    Thaokar, Sanjay F.; Patel, Dinesh M.; Patel, Manish P.; Patel, Ranjan G.

    2007-01-01

    3-Amino-6-methyl-1H- pyrazolo [3, 4-B] quinoline was synthesized in good yield. Monoazo compounds were prepared using this intermediate as diazo component with various heterocyclic coupling components. All the azo compounds were characterized by their percentage yield, melting point, elemental analysis, UV-visible spectra, IR-spectra and dyeing performance on nylon and polyester fibres and by their antibacterial activity against gram positive and gram negative bacteria. (author)

  6. N-Heterocyclic Carbene-Catalyzed Olefination of Aldehydes with Vinyliodonium Salts To Generate α,β-Unsaturated Ketones.

    Rajkiewicz, Adam A; Kalek, Marcin

    2018-04-06

    An organocatalyzed metal-free, direct olefination of aldehydes with vinyliodonium salts has been achieved by an N-heterocyclic carbene-promoted C-H bond activation. The reaction proceeds under very mild conditions, delivering a range of (hetero)aryl-vinyl ketones in good yields. The retention of the double bond configuration is uniformly observed, and the application of 2-methoxyphenyl auxiliary group in iodonium salts secures a complete selectivity of the vinyl transfer.

  7. Determination of acid-base dissociation constants of very weak zwitterionic heterocyclic bases by capillary zone electrophoresis

    Ehala, Sille; Grishina, Anastasia; Sheshenev, Andrey; Lyapkalo, Ilya; Kašička, Václav

    2010-01-01

    Roč. 1217, - (2010), s. 8048-8053 ISSN 0021-9673 R&D Projects: GA ČR(CZ) GA203/08/1428; GA ČR(CZ) GA203/09/0675 Institutional research plan: CEZ:AV0Z40550506 Keywords : acidity constant * capillary zone electrophoresis * zwitterionic heterocyclic bases Subject RIV: CC - Organic Chemistry Impact factor: 4.194, year: 2010

  8. Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

    Manzini, Simone; Urbina Blanco, Cé sar A.; Nelson, David J.; Poater, Albert; Lebl, Tomas; Meiries, Sé bastien; Slawin, Alexandra M.Z.; Falivene, Laura; Cavallo, Luigi; Nolan, Steven P.

    2015-01-01

    The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

  9. Agir sur la langue pour agir sur le monde : Micropolitiques linguistiques autogérées du genre dans les brochures libertaires

    Abbou, Julie

    2015-01-01

    La dimension agissante de la langue sur le monde entraîne avec elle, comme un appel d'air, l'action sur la langue elle-même, et l'action sur la langue n'est jamais loin de se faire action politique. Les politiques linguistiques de féminisation en sont un exemple, où l'action politique se concentre sur la catégorisation du genre. Dans de nombreux cas, la politique linguistique se fait planification linguistique, cherchant de nouvelles normes. Dans de nombreux cas, mais pas toujours. Il existe ...

  10. Insight into eukaryotic topoisomerase II-inhibiting fused heterocyclic compounds in human cancer cell lines by molecular docking.

    Taskin, T; Yilmaz, S; Yildiz, I; Yalcin, I; Aki, E

    2012-01-01

    Etoposide is effective as an anti-tumour drug by inhibiting eukaryotic DNA topoisomerase II via establishing a covalent complex with DNA. Unfortunately, its wide therapeutic application is often hindered by multidrug resistance (MDR), low water solubility and toxicity. In our previous study, new derivatives of benzoxazoles, benzimidazoles and related fused heterocyclic compounds, which exhibited significant eukaryotic DNA topoisomerase II inhibitory activity, were synthesized and exhibited better inhibitory activity compared with the drug etoposide itself. To expose the binding interactions between the eukaryotic topoisomerase II and the active heterocyclic compounds, docking studies were performed, using the software Discovery Studio 2.1, based on the crystal structure of the Topo IIA-bound G-segment DNA (PDB ID: 2RGR). The research was conducted on a selected set of 31 fused heterocyclic compounds with variation in structure and activity. The structural analyses indicate coordinate and hydrogen bonding interactions, van der Waals interactions and hydrophobic interactions between ligands and the protein, as Topo IIA-bound G-segment DNA are responsible for the preference of inhibition and potency. Collectively, the results demonstrate that the compounds 1a, 1c, 3b, 3c, 3e and 4a are significant anti-tumour drug candidates that should be further studied.

  11. Nitrogen, oxygen or sulfur containing heterocyclic compounds as analgesic drugs used as modulators of the nitroxidative stress.

    Salat, Kinga; Moniczewski, Andrzej; Librowski, Tadeusz

    2013-03-01

    Numerous lines of evidence suggest that heterocyclic compounds used as analgesic, anti-inflammatory and anti-migraine agents can be potent regulators of the nitroxidative stress and targeting free nitrogen and oxygen radicals is a very promising strategy for future pain management. Both classical analgesics (nonsteroidal anti-inflammatory drugs, opioid drugs) and many analgesic adjuvants, including desipramine, duloxetine, fluoxetine, paroxetine, escitalopram, phenytoin or carbamazepine and α-lipoic acid can modulate the balance between pro-oxidant and antioxidant processes in the mammalian tissues and these properties of drugs such as indomethacin, meloxicam, tenoxicam, valdecoxib or some metabolites of analgesic drugs formed by the activity of tissue peroxidases may contribute to their clinical efficacy and drug-related toxic effects, including gastrointestinal ulcers, hepatic failure, agranulocytosis, aplastic anemia, neutropenia, opiate-induced hyperalgesia and tolerance. The antioxidant capacities of novel heterocyclic compounds, including the compounds acting either by prevention of formation or catalyzed decomposition of peroxynitrite anion (ONOO-), namely the peroxynitrite decomposition catalysts or as superoxide (O2 •-)-scavengers which are the functional mimetics of superoxide dismutase (SOD) enzymes (SODm), as well as the derivatives of 6-nitro-3,4-methylenedioxyphenyl-Nacylhydrazone (LASSBio-881) or γ-butyrolactone (LPP1, BM113, BM113A, BM138 and BM138A) are also discussed as potent and promising future heterocyclic analgesics.

  12. Auranofin and N-heterocyclic carbene gold-analogs are potent inhibitors of the bacteria Helicobacter pylori.

    Owings, Joshua P; McNair, Nina N; Mui, Yiu Fung; Gustafsson, Tomas N; Holmgren, Arne; Contel, Maria; Goldberg, Joanna B; Mead, Jan R

    2016-07-01

    Auranofin is an FDA-approved gold-containing compound used for the treatment of rheumatoid arthritis. Recent reports of antimicrobial activity against protozoa and bacteria indicate that auranofin targets the reductive enzyme thioredoxin reductase (TrxR). We evaluated auranofin as well as five auranofin analogs containing N-heterocyclic carbenes (instead of the triethylphosphane present in auranofin) and five gold-carbene controls for their ability to inhibit or kill Helicobacter pylori in vitro Auranofin completely inhibited bacterial growth at 1.2 μM. Purified H. pylori TrxR was inhibited by auranofin in a cell-free assay (IC50 ∼88 nM). The most active gold(I)-N-heterocyclic carbene compounds exhibited MICs comparable to auranofin against H. pylori (2 μM), while also exhibiting lower toxicities for human embryonic kidney cells (HEK-293T cells). Median toxic concentrations (TC50) were 13-20-fold higher compared to auranofin indicating that they were less cytotoxic. The N-heterocyclic carbene analogs maybe well tolerated, but further evaluation is needed in vivo Finally, auranofin was synergistic with the antibiotic amoxicillin, suggesting that targeting both the reductive enzyme TrxR and cell wall synthesis may be effective against H. pylori infections. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  13. CARACTERIZACIÓN DEL CONSUMO DE HORTALIZAS EN LAS FAMILIAS DEL SUR-SUR DE COSTA RICA

    Alexis Villalobos-Monge

    2013-01-01

    Full Text Available El objetivo de este trabajo fue determinar los diferentes aspectos cuantitativos y cualitativos que explican la cultura de consumo actual de hortalizas en las familias residentes en la zona sur-sur de Costa Rica. Este trabajo expone resultados relacionados a la caracterización realizada en el 2011 en familias residentes en la denominada zona sur-sur de Costa Rica sobre la cultura de consumo de productos hortícolas. Se aplicaron cuestionarios a una muestra estratificada de familias; lo que permitió establecer la valoración de los precios de mercado, por parte de las familias, para consumir estos alimentos, donde se determinó un valor máximo de US$1,74 millones por semana. Los principales rubros de consumo de acuerdo al valor pagado fueron el tomate, la papa, el plátano, la cebolla y el brócoli, para citar los cinco principales. También fue posible establecer valoraciones cualitativas sobre el consumo de estos productos; por ejemplo se determinó que para el 71,2% de las familias, la frescura representa la característica de mayor valor, además, el principal sitio donde los núcleos familiares realizan las compras de estos alimentos corresponde a supermercados (38,4% de los casos.

  14. Nitrogen treatment from digestat of biogas plants in a moving bed biofilm reactor; Projet de recherche pilote. Traitement de l'azote des digestats issus d'installations de biogaz au moyen d'un reacteur a biofilm sur support mobile - Rapport final

    Roches, S.; Bakx, T.; Membrez, Y. [EREP SA, Aclens (Switzerland); Baggenstos, M.; Chappaz, A. [Wabag Water Technology Ltd, Winterthur (Switzerland); Holliger, Ch. [Swiss Federal Institute of Technology, EPFL, Laboratory for Environmental Biotechnology, Lausanne (Switzerland)

    2010-11-15

    Ammonia emissions are a source for polluting ecosystems, causing in particular acidification and eutrophication of the affected areas. In Switzerland 90% of the atmospheric ammonia emissions are due to agriculture, mostly during storage and use of animal manures and slurries. Anaerobic digestion of these manures and slurries produces renewable energy and stabilises the agricultural effluents. However, it does not solve the ammonia problem; on the contrary, it releases an additional amount of ammonium while mineralizing a large part of the organic nitrogen. A previous study dealing with the biological removal of ammonia from digested manures was conducted at the Laboratory of Environmental Biotechnology, EPFL. It has shown that it is possible to obtain simultaneously a conversion of ammonium and nitrogen removal in a same continuously aerated aerobic reactor, using a mobile support for fixing the biomass. The obtained efficiencies were high, with 90% of the ammonium being converted of which 80% as N{sub 2}-gas. This current study proposed to test the process at pilot scale, to evaluate the transferability of the technique to a full-scale application and to determine the operating parameter. The results are as follows: (i) It is possible to obtain high nitrification and denitrification rates without pre-treating the digestat or adding a carbon source; (ii) Biochemical reactions are extremely sensitive to the oxygenation rate, which in turn is very sensitive to the liquid characteristics in the reactor, such as the dry matter content. It fairly complicates maintaining simultaneous nitrification and denitrification; (iii) At a minimum hydraulic residence time of 4 days, over 90% of the ammonium is converted and 85% of it is removed. These results provide the basic design parameters for a full-scale installation. Depending on the performance desired, it would have a volume going from 30 to 60 m{sup 3} for a 400 m{sup 3} digester. The aeration rate would be between 300 and 600 Nm{sup 3}/h while the annual costs are estimated between CHF 36,000 and CHF 50,000. This amount, which includes amortisation and usage charges, corresponds to a range between 12 and 20 CHF per m{sup 3} of effluent treated, which is relatively low compared to conventional biological treatment systems. (authors)

  15. Precise measurement of the absolute fluorescence yield of nitrogen in air. Consequences on the detection of ultra-high energy cosmic rays; Mesure precise du rendement absolu de la fluorescence de l'azote dans l'air. Consequences sur la detection des rayons cosmiques d'ultra-haute energie

    Lefeuvre, G

    2006-07-15

    The study of the energy spectrum of ultra-high energy cosmic rays (E > 10{sup 20} eV) requires to determine the energy with much more precision than what is currently achieved. The shower of particles created in the atmosphere can be detected either by sampling particle on the ground, or by detecting the fluorescence induced by the excitation of nitrogen by shower electrons. At present, the measurement of the fluorescence is the simplest and the most reliable method, since it does not call upon hadronic physics laws at extreme energies, a field still inaccessible to accelerators. The precise knowledge of the conversion factor between deposited energy and the number of fluorescence photons produced (the yield) is thus essential. Up to now, it has been determined with an accuracy of 15 % only. This main goal of this work is to measure this yield to better than 5 per cent. To do this, 1 MeV electrons from a radioactive source excite nitrogen of the air. The accuracy has been reached thanks to the implementation of a new method for the absolute calibration of the photomultipliers detecting the photons, to better than 2 per cent. The fluorescence yield, measured and normalized to 0.85 MeV, 760 mmHg and 15 Celsius degrees, is (4.23 {+-} 0.20) photons per meter, or (20.46 {+-} 0.98) photons per deposited MeV. In addition, and for the first time, the absolute fluorescence spectrum of nitrogen excited by a source has been measured with an optical grating spectrometer. (author)

  16. Numerical and experimental study of the influence of the operational parameters on the formation mechanisms of oxides of nitrogen during the combustion of mixtures of cellulosic and plastic materials; Etude experimentale et numerique de l'influence des parametres operatoires sur les mecanismes de formation des oxydes d'azote lors de la combustion de melanges de materiaux cellulosiques et plastiques

    Andzi Barhe, T.

    2004-10-15

    The current thesis was performed within a collaboration between the Laboratoire de Combustion et de Detonique (LCD of the University of Poitiers) and the Laboratoire de Physique et de Chimie d'Environnement (LPCE) of the University of Ouagadougou. It was financed by Agency for Environment and Energy Management (ADEME). The principle object of this study is the optimisation of the combustion process during the incineration of waste. This optimisation is aimed at the reduction of the polluting emissions, principally CO and NO, during the incineration of cellulosic and plastic materials. It involves the analysis of the influence of the operational parameters on the polluting emissions and the control of reaction mechanisms of formation and reduction of these pollutants during the combustion process. Consequently, the study was performed in two parts: an experimental part and a numerical part. The experimental part was realised using a fixed bed counterflow reactor. This setup simulates the combustion within an industrial waste incinerator. The reactor allows the combustion of a vertical layer of waste mixture (wood, cardboard, PET, polyamide) to be followed. Three model mixtures representative of the makeup of household waste were studied in order to determine the influence of the composition of the waste on the emission of pollutants (CO and NO). The obtained results show that this parameter has a practically negligible influence within the tested parameter range. Consequently the formation of pollutants depends on the operating parameters - the equivalence ratio and the temperature. A numerical study of the influence of these parameters in order to show their impact on the mechanisms of pollutant formation and to determine the chemical mechanisms involved in the formation of oxides of nitrogen. The numerical study was performed with software developed at the LCD. This programme based on a detailed chemical model coupled to a simple physical model. It uses the calculation code CHEMKIN. It permits the simulation of combustion process within the gaseous zone of the fixed bed reactor. The programme is initialized with the results of the analysis of the pyrolysis which had previously been performed at the LCD on the materials which make up the model waste mixture. The pyrolysis products identified during this study are: HCN, NH{sub 3}, NO, NO{sub 2}, CO and light hydrocarbons. The results show that the simulation enables the determination of reactional mechanisms of the formation and reduction of oxides of nitrogen in the three combustion regimes identified during the experimental study. For each of the three regimes, a study of the impact of the combustion parameters on the yield of NO was performed. It can be seen that the response to the parameters is itself heavily dependent on the combustion regime. (author)

  17. Regioselective Aziridination of Silyl Allenes and Application for the Synthesis of New Heterocycles

    Burke, Eileen Grace

    Rhodium catalyzed aziridination of homoallenic sulfamates has proven to be a successful first step in the synthesis of a diverse array of complex nitrogenated motifs. Previously, however, the resultant methyleneaziridine was limited to the exocyclic isomer. In this work, a reliable direction strategy for the formation of the endocyclic isomer was identified. Placement of a silicon group on the allene so that its C - Si bond is co-planar to the distal pi-bond allowed for stabilization of the developing positive charge during aziridination, and therefore selective activation to form the endocyclic methyleneaziridine. This strategy proved robust, and endocyclic methyleneaziridines were formed in high yields with exclusive formation of the desired isomer regardless of the substitution of the allene. With the endocyclic isomer now readily available, its reactivity could be explored. First, the endocyclic methyleneaziridine was applied to the synthesis of densely functionalized, nitrogen containing motifs. In comparison with their exocyclic counterparts, the endocyclic methyleneaziridines were found to have differing reactivity. The olefin could be epoxidized using meta-chloroperoxybenzoic acid (mCPBA), and the resulting spirocyclic intermediate rapidly rearranged to an azetidin-3-one. This synthesis of the highly substituted fourmembered heterocycle represented a novel approach to these motifs, and was found to be both flexible, and to selectively form a single diastereomer. Additional derivatization of these scaffolds gave a diverse array of complex products. Further use of the endocyclic methyleneaziridine focused not on the complexity of the product motif but rather on its utility. The remaining silyl group could be eliminated upon reaction with a fluoride source, triggering the formation of an alkyne and resultant opening of the aziridine. This strained heterocyclic alkyne and its synthesis represent a new addition to the field of strained alkyne synthesis. Uniquely

  18. Accumulation of 19 environmental phenolic and xenobiotic heterocyclic aromatic compounds in human adipose tissue.

    Wang, Lei; Asimakopoulos, Alexandros G; Kannan, Kurunthachalam

    2015-05-01

    The extensive use of environmental phenols (e.g., bisphenol A) and heterocyclic aromatic compounds (e.g., benzothiazole) in consumer products as well as widespread exposure of humans to these compounds have been well documented. Biomonitoring studies have used urinary measurements to assess exposures, based on the assumption that these chemicals are metabolized and eliminated in urine. Despite the fact that some of these chemicals are moderately lipophilic, the extent of their accumulation in adipose fat tissues has not been convincingly demonstrated. In this study, human adipose fat samples (N=20) collected from New York City, USA, were analyzed for the presence of environmental phenols, including bisphenol A (BPA), benzophenone-3 (BP-3), triclosan (TCS), and parabens, as well as heterocyclic aromatic compounds, including benzotriazole (BTR), benzothiazole (BTH), and their derivatives. BPA and TCS were frequently detected in adipose tissues at concentrations (geometric mean [GM]: 3.95ng/g wet wt for BPA and 7.21ng/g wet wt for TCS) similar to or below the values reported for human urine. High concentrations of BP-3 were found in human adipose tissues (GM: 43.4; maximum: 4940ng/g wet wt) and a positive correlation between BP-3 concentrations and donor's age was observed. The metabolite of parabens, p-hydroxybenzoic acid (p-HB), also was found at elevated levels (GM: 4160; max.: 17,400ng/g wet wt) and a positive correlation between donor's age and sum concentration of parabens and p-HB were found. The GM concentrations of BTR and BTH in human adipose tissues were below 1ng/g, although the methylated forms of BTR (i.e., TTR and XTR) and the hydrated form of BTH (i.e., 2-OH-BTH) were frequently detected in adipose samples, indicating widespread exposure to these compounds. Our results suggest that adipose tissue is an important repository for BP-3 and parabens, including p-HB, in the human body. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Sur un deplacement de valeurs: traire et tirer

    André Burger

    1972-12-01

    Full Text Available L'étymologie de firer est inconnue. Celie que le regretté W. von Wart burg a ern pouvoir avancer est inacceptable: firer serait sorti de marty rier par la grâce d'une fausse coupure mar tirier. Il est plus qu'improbable que cette «étymologie populaire» eût pu se produire si la langue ne possédait pas au préalable un verbe tirier. Au surplus aucun fait n'appuie cette hypothèse. Le FEW, t. VI, 1, p. 396, donne bien pour firer le sens de «torturer sur un treteam>, au XIIIe siècle, et p. 403, «démembrer en faisant tirer les quatre membles par des chevaux» et «torturer (qn en l'étendant sur un tréteau” au XIVe siècle; ces sens sont évidemment trop tardifs pour permettre des conclusions sur l'origine de firer, d'autant plus qu'ils s'expliquent sans peine par la valeur normale du mot, attesté dès la Chanson de Roland, sans aucun rapport avec martirie, mot savant de clerc, qui, dans le même texte s'applique deux fois sur quatre exemples aux Sarrasins, vv. 501 et 1467, où il ne signifie pas «martyre» mais <sur son étymologie et non sur les textes, que tirer aurait à l'origine »einen starken affektiven unterton« (FEW XIII, 2, p. 185. L'étude des exemples de la Chanson de Roland, confrontés avec ceux de traire, nons amènera à une conclusion toute différente.

  20. Polar and non-polar heterocyclic amines in cooked fish and meat products and their corresponding pan residues.

    Skog, K; Augustsson, K; Steineck, G; Stenberg, M; Jägerstad, M

    1997-06-01

    Fourteen cooked dishes with their corresponding pan residues were analysed for polar and non-polar heterocyclic amines using HPLC. The choice of foods, including beef, pork, poultry, game, fish, egg and sausages, was based on an investigation of an elderly population in Stockholm participating in an analytical epidemiological case-control study on cancer risks after intake of heterocyclic amines. The food items were prepared using normal household cooking practices, and to reflect the wide range of surface browning of the cooked dishes that would be encountered in this population, four cooking temperatures were used in the range 150-225 degrees C. For all food samples, the total amount of heterocyclic amines formed at 150 degrees C was less than 1 ng/g cooked product, and at 175 degrees C less than 2 ng/g. The highest concentrations of heterocyclic amines were detected in fillet of pork, reindeer meat and chicken breast fried at 200 and 225 degrees C and their corresponding pan residues. The total sum of 2-amino-3,8-dimethylimidazo-[4,5-f]quinoxaline, 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine was about 1 microgram per 100 g portion (including pan residues) for reindeer meat and chicken breast, and between 1.9 and 6.3 micrograms per 100-g portion for fillet of pork. PhIP was the most abundant heterocyclic amine, identified in 73 of 84 samples, and the highest concentration of PhIP, 32.0 ng/g, was found in the pan residue from fillet of pork cooked at 225 degrees C. The non-polar heterocyclic amines 3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole and 3-amino-1-methyl-5H-pyrido[4,3-b]indole were detected in the range of 0.5-7.4 ng/g in most foods cooked at 225 degrees C, and also in meat sauce prepared at 200 and 175 degrees C. The other heterocyclic amines tested for: 2-amino-3-methylimidazo-[4,5-f]quinoline, 2-amino-3,4-dimethylimidazo[4,5-f]quinoline, 2-amino-6-methyl-pyrido-[1,2-a:3',2'-d]-imidazole and 2

  1. Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles

    Novak, Maria S.; Bü chel, Gabriel E.; Keppler, Bernhard K.; Jakupec, Michael A.

    2016-01-01

    Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed.

  2. Sulforaphane Analogues with Heterocyclic Moieties: Syntheses and Inhibitory Activities against Cancer Cell Lines

    Ye-Hui Shi

    2016-04-01

    Full Text Available Recent studies have shown that sulforaphane (SFN selectively inhibits the growth of ALDH+ breast cancer stem-like cells.Herein, a series of SFN analogues were synthesized and evaluated against breast cancer cell lines MCF-7 and SUM-159, and the leukemia stem cell-like cell line KG-1a. These SFN analogues were characterized by the replacement of the methyl group with heterocyclic moieties, and the replacement of the sulfoxide group with sulfide or sulfone. A growth inhibitory assay indicated that the tetrazole analogs 3d, 8d and 9d were significantly more potent than SFN against the three cancer cell lines. Compound 14c, the water soluble derivative of tetrazole sulfide 3d, demonstrated higher potency against KG-1a cell line than 3d. SFN, 3d and 14c significantly induced the activation of caspase-3, and reduced the ALDH+ subpopulation in the SUM159 cell line, while the marketed drug doxrubicin(DOX increased the ALDH+ subpopulation.

  3. Serotonergic 5-HT6 Receptor Antagonists: Heterocyclic Chemistry and Potential Therapeutic Significance.

    Bali, Alka; Singh, Shalu

    2015-01-01

    The serotonin 5-HT(6) receptor (5- HT(6)R) is amongst the recently discovered serotonergic receptors with almost exclusive localization in the brain. Hence, this receptor is fast emerging as a promising target for cognition enhancement in central nervous system (CNS) diseases such as Alzheimer's disease (cognitive function), obesity, schizophrenia and anxiety. The last decade has seen a surge of literature reports on the functional role of this receptor in learning and memory processes and investigations related to the chemistry and pharmacology of 5-HT(6) receptor ligands, especially 5- HT(6) receptor antagonists. Studies show the involvement of multiple neurotransmitter systems in cognitive enhancement by 5-HT(6)R antagonists including cholinergic, glutamatergic, and GABAergic systems. Several of the 5-HT(6)R ligands are indole based agents bearing structural similarity to the endogenous neurotransmitter serotonin. Based on the pharmacophoric models proposed for these agents, drug designing has been carried out incorporating various heterocyclic replacements for the indole nucleus. In this review, we have broadly summarized the medicinal chemistry and current status of this fairly recent class of drugs along with their potential therapeutic applications.

  4. Adsorptive stripping voltammetric behaviour of copper complexes of some heterocyclic azo compounds.

    Farias, P A; Ferreira, S L; Ohara, A K; Bastos, M B; Goulart, M S

    1992-10-01

    Controlled adsorptive accumulation of copper complexed with TAN, TAC, TAR and TAM (heterocyclic azo-compounds) on a static mercury drop electrode provides the basis for the direct stripping measurement of this element in the nanomolar concentration level. The ligand TAN exhibited great sensitivity and better separation of the peak current of the ligand in relation to the complex. The reduction current of adsorbed complex ions of copper is measured by linear scan cathodic stripping voltammetry, preceded by a period of accumulation of a few minutes. The peak potential is at approximately -0.37 V vs. Ag/AgCl. Optimal experimental parameters were found to be a TAN concentration of 1 x 10(-5)M, an accumulation potential of -0.22 V, and a solution pH of 3.7 (acetate buffer). The detection limit is 0.8nM after a 5-min accumulation with a stirred solution, and the response is linear up to 50 mug/l. Many common cations and anions do not interfere in the determination of copper. The interference of titanium is eliminated by addition of fluoride ion. Results are reported for a fresh water sample.

  5. Flexible Enantioselectivity of Tryptophanase Attributable to Benzene Ring in Heterocyclic Moiety of D-Tryptophan

    Akihiko Shimada

    2012-05-01

    Full Text Available The invariance principle of enzyme enantioselectivity must be absolute because it is absolutely essential to the homochiral biological world. Most enzymes are strictly enantioselective, and tryptophanase is one of the enzymes with extreme absolute enantioselectivity for L-tryptophan. Contrary to conventional knowledge about the principle, tryptophanase becomes flexible to catalyze D-tryptophan in the presence of diammonium hydrogenphosphate. Since D-amino acids are ordinarily inert or function as inhibitors even though they are bound to the active site, the inhibition behavior of D-tryptophan and several inhibitors involved in this process was examined in terms of kinetics to explain the reason for this flexible enantioselectivity in the presence of diammonium hydrogenphosphate. Diammonium hydrogenphosphate gave tryptophanase a small conformational change so that D-tryptophan could work as a substrate. As opposed to other D-amino acids, D-tryptophan is a very bulky amino acid with a benzene ring in its heterocyclic moiety, and so we suggest that this structural feature makes the catalysis of D-tryptophan degradation possible, consequently leading to the flexible enantioselectivity. The present results not only help to understand the mechanism of enzyme enantioselectivity, but also shed light on the origin of homochirality.

  6. Biological properties of novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles

    Novak, Maria S.

    2016-03-09

    Since the discovery that nitric oxide (NO) is a physiologically relevant molecule, there has been great interest in the use of metal nitrosyl compounds as antitumor pharmaceuticals. Particularly interesting are those complexes which can deliver NO to biological targets. Ruthenium- and osmium-based compounds offer lower toxicity compared to other metals and show different mechanisms of action as well as different spectra of activity compared to platinum-based drugs. Novel ruthenium- and osmium-nitrosyl complexes with azole heterocycles were studied to elucidate their cytotoxicity and possible interactions with DNA. Apoptosis induction, changes of mitochondrial transmembrane potential and possible formation of reactive oxygen species were investigated as indicators of NO-mediated damage by flow cytometry. Results suggest that ruthenium- and osmium-nitrosyl complexes with the general formula (indazolium)[cis/trans-MCl4(NO)(1H-indazole)] have pronounced cytotoxic potency in cancer cell lines. Especially the more potent ruthenium complexes strongly induce apoptosis associated with depolarization of mitochondrial membranes, and elevated reactive oxygen species levels. Furthermore, a slight yet not unequivocal trend to accumulation of intracellular cyclic guanosine monophosphate attributable to NO-mediated effects was observed.

  7. A compendium of cyclic sugar amino acids and their carbocyclic and heterocyclic nitrogen analogues.

    Risseeuw, Martijn; Overhand, Mark; Fleet, George W J; Simone, Michela I

    2013-10-01

    This compendium focuses on functionalised sugar amino acids (SAAs) and their 3- to 6-membered nitrogen heterocyclic and carbocyclic analogues. The main benefit of using SAAs and their related nitrogen and carbon congeners in the production of peptidomimetics and glycomimetics is that their properties can be readily altered via modification of their ring size, chemical manipulation of their numerous functional groups and fine-tuning of the stereochemical arrangement of their ring substituents. These building blocks provide access to hydrophilic and hydrophobic peptide isosteres whose physical properties allow entry to a region of chemotherapeutic space which is still under-explored by medicinal chemists. These building blocks are also important in providing amino acids whose inherent conformational bias leads to predisposition to secondary structure upon oligomerisation in relatively short sequences. These foldamers, particularly those containing ω-amino acids, provide an additional opportunity to expand access to the control of structures by artificial peptides. The synthesis and biological evaluation of these building blocks in glycomimetics and peptidomimetics systems keep expanding the reach of the glycosciences to the medical sciences, provide a greater outlook onto the wide range of cellular functions of saccharides and their derivatives involved and greater insight into the nature of oligosaccharide and protein folding.

  8. High intake of heterocyclic amines from meat is associated with oxidative stress.

    Carvalho, A M; Miranda, A M; Santos, F A; Loureiro, A P M; Fisberg, R M; Marchioni, D M

    2015-04-28

    High meat intake has been related to chronic diseases such as cancer and CVD. One hypothesis is that heterocyclic amines (HCA), which are formed during the cooking process of meat, can generate reactive species. These compounds can cause oxidation of lipids, proteins and DNA, resulting in oxidative stress, cell damage and loss of biological function. This association has been seen in vitro; however, it remains unclear in vivo. The aim of the present study was to investigate the association between oxidative stress and HCA intake, and oxidative stress and meat intake. Data were from the Health Survey for Sao Paulo--ISA-Capital (561 adult and elderly). Food intake was estimated by one 24-h dietary recall (24HR) complemented by a detailed FFQ with preferences of cooking methods and level of doneness for meat. HCA intake was estimated linking the meat from the 24HR to a database of HCA. Oxidative stress was estimated by malondialdehyde (MDA) concentration in the plasma, after derivatisation with thiobarbituric acid and quantification by HPLC/diode array. Analyses were performed using multivariate logistic regressions adjusted for smoking, sex, age, BMI, skin colour, energy intake, fruit and vegetable intake, and physical activity. A positive association between HCA intake and MDA concentration (OR 1·17; 95% CI 1·01, 1·38) was observed, showing that HCA from meat may contribute to increase oxidative stress, and may consequently increase the risk of chronic diseases.

  9. The Reactions of Nitrogen Heterocycles with Acrolein: Scope and Prebiotic Significance

    Cleaves, H. James

    2002-12-01

    It has been suggested that life began with a self-replicating RNA molecule. However, after much research into the prebiotic synthesis of RNA, the difficulties encountered have lead some to hypothesize that RNA was preceded by a simpler molecule, one more easily synthesized prebiotically. Many of the proposed alternative molecules are based on acrolein, since it reacts readily with nucleophiles, such as the nucleobases, via Michael addition and is readily synthesized from formaldehyde and acetaldehyde. Reports regarding the reactions of nucleobases with concentrated acrolein solutions suggest that this is a plausible reaction mechanism, though there are also reports that the "incorrect" isomers are obtained. The scope and kinetics of the reaction of acrolein with various nitrogen heterocycles are reported here. Reactions of pyrimidines often give N1 adducts as the major products. Reactions of purines often give N9 adducts in good yield. The reactions are rapid under neutral to slightly alkaline conditions, and proceed at low temperatures and dilutions. The implications of these findings for the origin of life are discussed.

  10. Occurrence of heterocyclic amines in several home-cooked meat dishes of the Spanish diet.

    Busquets, R; Bordas, M; Toribio, F; Puignou, L; Galceran, M T

    2004-03-25

    Heterocyclic amines (HAs) were determined in several of the most frequently eaten meat dishes in Spain such as fried beef hamburger, fried pork loin, fried chicken breast, fried pork sausages, griddled chicken breast, griddled lamb steak and griddled beef steak. All of the products tested were household cooked. The HAs were analysed in the selected meat dishes using an analytical method based on solid-phase extraction followed by liquid chromatography coupled to tandem mass spectrometry. DMIP, MeIQx, 4,8-DiMeIQx, Norharman, Harman, PhIP, Trp-P-1, AalphaC and MeAalphaC were the amines most frequently found at concentrations of up to 47 ng g(-1) of cooked meat. Glu-P-2, IQ, MeIQ, Glu-P-1, 7,8-DiMeIQx and Trp-P-2 were only found in a few of the meat dishes and their concentrations were lower than 1 ng g(-1) of cooked meat. The highest amounts of HAs, especially PhIP and DMIP, were formed in fried chicken breast and the lowest were formed in fried beef hamburger and in fried pork sausages. Daily intake of HAs in Spain was estimated at 606 ng of mutagenic HAs per capita and day, DMIP and PhIP being the main contributors.

  11. Highly efficient blue OLEDs based on diphenylaminofluorenylstyrenes end-capped with heterocyclic aromatics

    Oh, Suhyun [Department of Chemistry, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Lee, Kum Hee; Kim, Young Kwan [Department of Information Display, Hongik University, Seoul 121-791 (Korea, Republic of); Yoon, Seung Soo, E-mail: ssyoon@skku.edu [Department of Chemistry, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

    2012-10-15

    In this paper, we have designed four diphenylaminofluorenylstyrene derivatives end-capped with heterocyclic aromatic groups, such as 9-phenylcabazole, 4-dibenzofuran, 2-benzoxazole, 2-quinoxaline, respectively. These materials showed blue to red fluorescence with maximum emission wavelengths of 476–611 nm, respectively, which were dependent on the structural and electronic nature of end-capping groups. To explore the electroluminescent properties of these materials, multilayer OLEDs were fabricated in the following sequence: ITO/DNTPD (40 nm)/NPB (20 nm)/2% doped in MADN (20 nm)/Alq{sub 3} (40 nm)/Liq. (1 nm)/Al. Among those, a device exhibited a highly efficient blue emission with the maximum luminance of 14,480 cd/m{sup 2} at 9 V, the luminous efficiency of 5.38 cd/A at 20 mA/cm{sup 2}, power efficiency of 2.77 lm/W at 20 mA/cm{sup 2}, and CIE{sub x,y} coordinates of (0.147, 0.152) at 8 V, respectively.

  12. Metabolic activation of polycyclic and heterocyclic aromatic hydrocarbons and DNA damage: A review

    Xue Weiling; Warshawsky, David

    2005-01-01

    Polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic compounds (HACs) constitute a major class of chemical carcinogens present in the environment. These compounds require activation to electrophilic metabolites to exert their mutagenic or carcinogenic effects. There are three principal pathways currently proposed for metabolic activation of PAH and HAC: the pathway via bay region dihydrodiol epoxide by cytochrome P450 enzymes (CYPs), the pathway via radical cation by one-electron oxidation, and the ortho-quinone pathway by dihydrodiol dehydrogenase (DD). In addition to these major pathways, a brief description of a minor metabolic activation pathway, sulfonation, for PAHs that contain a primary benzylic alcoholic group or secondary hydroxyl group(s) is included in this review. The DNA damages caused through the reactive metabolites of PAH/HAC are described involving the DNA covalent binding to form stable or depurinating adducts, the formation of apurinic sites, and the oxidative damage. The review emphasizes the chemical/biochemical reactions involved in the metabolic processes and the chemical structures of metabolites and DNA adducts

  13. Degradation of phenolics, nitrogen-heterocyclics and polynuclear aromatic hydrocarbons in a rotating biological contactor.

    Jeswani, Hansa; Mukherji, Suparna

    2012-05-01

    The degradation of phenolics, heterocyclics and polynuclear aromatic hydrocarbons (PAHs) in a synthetic biomass gasifier wastewater with average COD of 1388 mg/L was studied in a three stage rotating biological contactor (RBC) using the pyrene degrader, Exiguobacterium aurantiacum and activated sludge consortia (1:3 v/v). As the organic loading rate (OLR) was varied from 3.3 to 14 g/m(2)/d, the COD removal ranged from 63.3% to 92.6%. Complete removal of all the constituents was observed at the lowest OLR of 3.3g/m(2)/d. At 24h hydraulic retention time (HRT) and OLR of 6.6g/m(2)/d complete removal of pyridine, quinoline and benzene and 85-96% removal of phenol, naphthalene, phenanthrene, fluoranthene and pyrene was observed. E. aurantiacum was found to be the dominant bacteria in the biofilm. Clark's model provided good fits to data for all the three stages of the RBC. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Study of molecular mechanisms of proapoptotic action of novel heterocyclic 4-thiazolidone derivatives

    Lesyk R. B.

    2012-04-01

    Full Text Available Aim. Mechanisms of induction of apoptosis signaling pathways in mammalian tumor cells treated by novel heterocyclic 4-thiazolidones with different side groups were studied. Methods. Annexin V/propidium iodide and DAPI (4',6-diamidino-2-phenylindole staining of cells, Western-blot analysis of specific proteins. Results. 4-Thiazolidone derivatives of various structure possess similar cytotoxic activity in vitro (²Ñ50 = 5 µM, and induce apoptosis in both leukemia (Jurkat, CCRF-CEM and carcinoma (MCF-7, MDA-MD-231 cells. Western-blot analysis of the expression of several proteins of apoptosis signaling showed that the structure of lateral groups of 4-thiazolidones may directly affect biological activity of these proteins in leukemia cells. In particular, compounds Les-3120 (pyrazoline-substituted thiazolidinone and Les-3166 (thiazolidinone-benzothiazole conjugate induced receptor-mediated apoptosis in Jurkat T-leukemia cells. 4-Iminothiazolidinone Les-3372 caused mitochondrial type apoptosis, mediated by AIF protein. Conclusions. Structure-functional relationships between the presence of specific side groups in novel 4-thiazolidones and the signaling apoptotic pathways induced by these compounds have been established. The obtained results allow designing new, «hybrid» compounds which can simultaneously induce more than one apoptotic pathway in tumor cells.

  15. Microwave Assisted Organic Synthesis of Heterocycles in Aqueous Media: Recent Advances in Medicinal Chemistry.

    Frecentese, Francesco; Saccone, Irene; Caliendo, Giuseppe; Corvino, Angela; Fiorino, Ferdinando; Magli, Elisa; Perissutti, Elisa; Severino, Beatrice; Santagada, Vincenzo

    2016-01-01

    Green chemistry is a discipline of great interest in medicinal chemistry. It involves all fields of chemistry and it is based on the principle to conduct chemical reactions protecting the environment at the same time, through the use of chemical procedures able to avoid pollution. In this context, water as solvent is a good choice because it is abundant, nontoxic, non-caustic, and non-combustible. Even if microwave assisted organic reactions in conventional solvents have quickly progressed, in the recent years medicinal chemists have focused their attention to processes deemed not dangerous for the environment, using nanotechnology and greener solvents as water. Several reports of reaction optimizations and selectivities, demonstrating the capability of microwave to allow the obtaining of increased yields have been recently published using water as solvent. In this review, we selected the available knowledge related to microwave assisted organic synthesis in aqueous medium, furnishing examples of the newest strategies to obtain useful scaffolds and novel derivatives for medicinal chemistry purposes. The intention of this review is to demonstrate the exclusive ability of MAOS in water as solvent or as co-solvent. For this purpose we report here the most representative applications of MAOS using water as solvent, focusing on medicinal chemistry processes leading to interesting nitrogen containing heterocycles with potential pharmaceutical applications.

  16. Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

    Chen, Guojian; Zhou, Yu; Wang, Xiaochen; Li, Jing; Xue, Shuang; Liu, Yangqing; Wang, Qian; Wang, Jun

    2015-06-01

    In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g-1) and large pore volumes (up to 0.90 cm3 g-1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4‧-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405- the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

  17. Synthesis and catalytic activity of N-heterocyclic silylene (NHSi) cobalt hydride for Kumada coupling reactions.

    Qi, Xinghao; Sun, Hongjian; Li, Xiaoyan; Fuhr, Olaf; Fenske, Dieter

    2018-02-20

    The electron-rich silylene Co(i) chloride 5 was obtained through the reaction of CoCl(PMe 3 ) 3 with chlorosilylene. Complex 5 reacted with 1,3-siladiazole HSiMe(NCH 2 PPh 2 ) 2 C 6 H 4 to give the silylene Co(iii) hydride 6 through chelate-assisted Si-H activation. To the best of our knowledge, complex 6 is the first example of Co(iii) hydride supported by N-heterocyclic silylene. Complexes 5 and 6 were fully characterized by spectroscopic methods and X-ray diffraction analysis. Complex 6 was used as an efficient precatalyst for Kumada cross-coupling reactions. Compared with the related complex 3 supported by only trimethylphosphine, complex 6 as a catalyst supported by both chlorosilylene and trimethylphosphine exhibits a more efficient performance for the Kumada cross-coupling reactions. A novel catalytic radical mechanism was suggested and experimentally verified. As an intermediate silylene cobalt(ii) chloride 6d was isolated and structurally characterized.

  18. Optoelectronic studies on heterocyclic bases of deoxyribonucleic acid for DNA photonics.

    El-Diasty, Fouad; Abdel-Wahab, Fathy

    2015-10-01

    The optoelectronics study of large molecules, particularly π-stacking molecules, such as DNA is really an extremely difficult task. We perform first electronic structure calculations on the heterocyclic bases of 2'-deoxyribonucleic acid based on Lorentz-Fresnel dispersion theory. In the UV-VIS range of spectrum, many of the optoelectronic parameters for DNA four bases namely adenine, guanine, cytosine and thymine are calculated and discussed. The results demonstrate that adenine has the highest hyperpolarizability, whereas thymine has the lowest hyperpolarizability. Cytosine has the lower average oscillator energy and the higher lattice energy. Thymine infers the most stable nucleic base with the lower phonon energy. Thymine also has the highest average oscillator energy and the lower lattice energy. Moreover, the four nucleic acid bases have large band gap energies less than 5 eV with a semiconducting behavior. Guanine shows the smallest band gap and the highest Fermi level energy, whereas adenine elucidates the highest band gap energy. Copyright © 2015. Published by Elsevier B.V.

  19. Synthesis of pyridine and isoquinoline labelled with 14C on the nitrogen heterocycle

    Robveille, Jacques

    1985-01-01

    This research thesis addresses the synthesis of derivatives of pyridine and isoquinoline labelled with carbon 14 ( 14 C) in the nitrogenated heterocycle as these compounds are of biological and pharmacological interest. The author aimed at developing rather general synthesis schemes which could be easily applied to the synthesis of radioactive compounds, and could produce, through a given synthesis way, the largest as possible family of differently substituted compounds. Different sources for labelled pyridine and isoquinoline have been used: dioxo-1,5 or their corresponding dioxins, substituted pentadienoic acids, derivatives of acrylic acid, and derivatives of cinnamic acid. Thus, three different synthesis processes have been developed to obtain 14 C labelled pyridine, and one of them is applied to the preparation of 14 C labelled isoquinoline. These synthesis processes can have a very general application, and allow different 14 C labelling positions to be envisaged. The possibility to obtain the same compounds but labelled with tritium can also be envisaged to obtain much higher specific activities [fr

  20. Effects of different types of soy sauce on the formation of heterocyclic amines in roasted chicken.

    Alam Shah, Syifaa; Selamat, Jinap; Haque Akanda, Md Jahurul; Sanny, Maimunah; Khatib, Alfi

    2018-05-01

    The objective of the study was to determine the effect of different types of soy sauce and marinating time on the formation of heterocyclic amines (HCAs) in roasted chicken. Chicken breast samples were marinated with sweet, salty, light and dark soy sauce at 0, 3, 6 and 12 h (control treatment was the chicken without marinade). The concentrations of free amino acids, sugars and creatinine were determined before roasting while HCA concentrations were determined after roasting. All types of soy sauce significantly increased (p ≤ 0.05) the concentration of HCAs in roasted chicken with increasing marinating time. The highest increment of total concentration of HCAs was found in samples marinated with light soy sauce (887%) followed by dark (375%), salty (193%) and sweet (169%) at 12 h. PhIP (2-amino-1-methyl-6-phenylimidazo(4,5-b)pyridine) showed a substantial reduction in samples only momentarily marinated with sweet, salty and dark soy sauce (0 h). Free amino acids were found to be more strongly correlated with the formation of HCAs than reducing sugars or creatinine.

  1. Reducing effect of artichoke extract on heterocyclic aromatic amine formation in beef and chicken breast meat.

    Tengilimoglu-Metin, Mercan Merve; Kizil, Mevlude

    2017-12-01

    The aim of this study was to investigate the inhibitory effect of different levels of artichoke extract (0, 0.5, and 1.0%) on the formation of heterocyclic aromatic amines (HAAs) in beef and chicken breast meat cooked by either pan-frying or oven-roasting. All meat samples were cooked at three different temperatures (150, 200, and 250°C) and the levels of 12 HAAs (IQ, IQx, MeIQ, MeIQx, 4,8-DiMeIQx, 7,8-DiMeIQx, PhIP, harman, norharman, AαC, MeAαC, and Trp-P-2) were assessed. The total HAA content in beef and chicken breast ranged from not detectable to 49.26ng/g, and not detectable to 83.06ng/g, respectively. The inhibitory effects of 0.5 and 1.0% artichoke extracts on total HAAs levels were found to be 6-46% and 25-98% in beef, and 5-97% and 14-95% in chicken breast, respectively. The present study showed that artichoke extracts could mitigate HAA formation especially in oven-roasted beef and chicken breast meat. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Synthesis, Antiproliferative, and Multidrug Resistance Reversal Activities of Heterocyclic α,β-Unsaturated Carbonyl Compounds.

    Sun, Ju-Feng; Hou, Gui-Ge; Zhao, Feng; Cong, Wei; Li, Hong-Juan; Liu, Wen-Shuai; Wang, Chunhua

    2016-10-01

    A series of heterocyclic α,β-unsaturated carbonyl compounds (1a-1d, 2a-2d, 3a-3d, 4a-3d, and 5a-5d) with 1,5-diaryl-3-oxo-1,4-pentadienyl pharmacophore were synthesized for the development of anticancer and multidrug resistance reverting agents. The antiproliferative activities were tested against nine human cancer cell lines. Approximately 73% of the IC50 values were below 5 μm, while 35% of these figures were submicromolar, and compounds 3a-3d with 4-trifluoro methyl in the arylidene benzene rings were the most potent, since their IC50 values are between 0.06 and 3.09 μm against all cancer cell lines employed. Meanwhile, their multidrug resistance reversal properties and cellular uptake were further examined. The data displayed that all of these compounds could reverse multidrug resistance, particularly, compounds 3a and 4a demonstrated both potent multidrug resistance reverting properties and strong antiproliferative activities, which can be taken as leading molecules for further research of dual effect agents in tumor chemotherapy. © 2016 John Wiley & Sons A/S.

  3. Fused Heterocyclic Compounds as Potent Indoleamine-2,3-dioxygenase 1 Inhibitors.

    Panda, Subhankar; Roy, Ashalata; Deka, Suman Jyoti; Trivedi, Vishal; Manna, Debasis

    2016-12-08

    Uncontrolled metabolism of l-tryptophan (l-Trp) in the immune system has been recognized as a critical cellular process in immune tolerance. Indoleamine 2,3-dioxygenase 1 (IDO1) enzyme plays an important role in the metabolism of a local l-Trp through the kynurenine pathway in the immune systems. In this regard, IDO1 has emerged as a therapeutic target for the treatment of diseases that are associated with immune suppression like chronic infections, cancer, and others. In this study, we synthesized a series of pyridopyrimidine, pyrazolopyranopyrimidine, and dipyrazolopyran derivatives. Further lead optimizations directed to the identification of potent compounds, 4j and 4l (IC 50 = 260 and 151 nM, respectively). These compounds also exhibited IDO1 inhibitory activities in the low nanomolar range in MDA-MB-231 cells with very low cytotoxicity. Stronger selectivity for the IDO1 enzyme (>300-fold) over tryptophan 2,3-dioxygenase (TDO) enzyme was also observed for these compounds. Hence, these fused heterocyclic compounds are attractive candidates for the advanced study of IDO1-dependent cellular function and immunotherapeutic applications.

  4. Studies on the cytotoxicity and anticancer performance of heterocyclic hypervalent organobismuth(III) compounds.

    Liu, Yong-Ping; Lei, Jian; Tang, Li-Wen; Peng, Yao; Au, Chak-Tong; Chen, Yi; Yin, Shuang-Feng

    2017-10-20

    Novel organobismuth(III) complex of 5H-dibenzo[c,f][1,5]oxabismocin-12(7H)-yl nitrate (C2) was synthesized and characterized by spectral and elemental analysis. It was compared with other five C,E,C-chelating (E = N, O, S) organobismuth(III) complexes against human adenocarcinoma alveolar basal epithelial cells (A549), human liver cancer cell line (SMCC7721), human gastric cancer cell line (SGC-7901), human colon adenocarcinoma cell line (SW480) and healthy human bronchial cell line (16HBE14o-) in vitro. It was found that C2 exhibited the best anticancer activity. Further mechanistic investigation indicated that toxicological activity of C2 was ascribable to apoptosis rather than anti-proliferative activity. Apoptosis was induced through up-regulating the level of Bcl-2/Bax as well as the activation of caspase-3. The results demonstrate that heterocyclic organobismuth(III) complexes of this type have great potential in the treatment of cancer. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  5. Measurement and ANN prediction of pH-dependent solubility of nitrogen-heterocyclic compounds.

    Sun, Feifei; Yu, Qingni; Zhu, Jingke; Lei, Lecheng; Li, Zhongjian; Zhang, Xingwang

    2015-09-01

    Based on the solubility of 25 nitrogen-heterocyclic compounds (NHCs) measured by saturation shake-flask method, artificial neural network (ANN) was employed to the study of the quantitative relationship between the structure and pH-dependent solubility of NHCs. With genetic algorithm-multivariate linear regression (GA-MLR) approach, five out of the 1497 molecular descriptors computed by Dragon software were selected to describe the molecular structures of NHCs. Using the five selected molecular descriptors as well as pH and the partial charge on the nitrogen atom of NHCs (QN) as inputs of ANN, a quantitative structure-property relationship (QSPR) model without using Henderson-Hasselbalch (HH) equation was successfully developed to predict the aqueous solubility of NHCs in different pH water solutions. The prediction model performed well on the 25 model NHCs with an absolute average relative deviation (AARD) of 5.9%, while HH approach gave an AARD of 36.9% for the same model NHCs. It was found that QN played a very important role in the description of NHCs and, with QN, ANN became a potential tool for the prediction of pH-dependent solubility of NHCs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Facile synthesis and antimicrobial evaluation of some new heterocyclic compounds incorporating a biologically active sulfamoyl moiety.

    Darwish, Elham S

    2014-01-01

    A facile and convenient synthesis of new heterocyclic compounds containing a sulfamoyl moiety suitable for use as antimicrobial agents was reported. The precursor 3-oxo-3-phenyl-N-(4-sulfamoylphenyl)propionamide was coupled smoothly with arenediazonium salt producing hydrazones which reacted with malononitrile or triethylorthoformate affording pyridazine and triazine derivatives, respectively. Also, the reactivity of the same precursor with DMF-DMA was followed by aminotriazole; aromatic aldehydes was followed by hydrazine hydrate, triethylorthoformate, or thiourea affording triazolo[1,5-a]pyrimidine, pyrazole, acrylamide, and dihydropyrimidine derivatives, respectively. On the other hand, treatment of the precursor propionamide with phenyl isothiocyanate and KOH in DMF afforded the intermediate salt which was treated with dilute HCl followed by 2-bromo-1-phenylethanone affording carboxamide derivative. While the same intermediate salt reacted in situ with chloroacetone, ethyl 2-chloroacetate, 3-(2-bromoacetyl)-2H-chromen-2-one, methyl iodide, or 2-oxo-N-phenylpropane hydrazonoyl chloride afforded the thiophene, ketene N,S-acetal, and thiadiazole derivatives, respectively. The structure of the new products was established based on elemental and spectral analysis. Antimicrobial evaluation of some selected examples from the synthesized products was carried out whereby four compounds were found to have moderate activities and one compound showed the highest activity.

  7. Photoprotective effect and acute oral systemic toxicity evaluation of the novel heterocyclic compound LQFM048.

    Vinhal, Daniela C; de Ávila, Renato Ivan; Vieira, Marcelo S; Luzin, Rangel M; Quintino, Michelle P; Nunes, Liliane M; Ribeiro, Antonio Carlos Chaves; de Camargo, Henrique Santiago; Pinto, Angelo C; Dos Santos Júnior, Helvécio M; Chiari, Bruna G; Isaac, Vera; Valadares, Marize C; Martins, Tatiana Duque; Lião, Luciano M; de S Gil, Eric; Menegatti, Ricardo

    2016-08-01

    The new heterocyclic derivative LQFM048 (3) (2,4,6-tris ((E)-ethyl 2-cyano-3-(4-hydroxy-3-methoxyphenyl)acrylate)-1,3,5-triazine) was originally designed through the molecular hybridization strategy from Uvinul® T 150 (1) and (E)-ethyl 2-cyano-3-(4hydroxy-3-methoxyphenyl)acrylate (2) sunscreens, using green chemistry approach. This compound was obtained in global yields (80%) and showed an interesting redox potential. In addition, it is thermally stable up to temperatures around 250°C. It was observed that LQFM048 (3) showed a low degradation after 150min of sunlight exposure at 39°C, whereas the extreme radiation conditions induced a considerable photodegradation of the LQFM048 (3), especially when irradiated by VIS and VIS+UVA. During the determination of sun protection factor, LQFM048 (3) showed interesting results, specially as in association with other photoprotective compounds and commercial sunscreen. Additionally, the compound (3) did not promote cytotoxicity for 3T3 fibroblasts. Moreover, it was not able to trigger acute oral systemic toxicity in mice, being classified as a compound with low acute toxicity hazard (2.000mg/kg>LD50compound synthesized using green chemistry approach is promising showing potential to development of a new sunscreen product with advantage of presenting redox potential, indicating antioxidant properties. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Kinetic behaviour of graft copolymerisation of nitrogenous heterocyclic monomer onto EB-irradiated ETFE films

    Paveswari Sithambaranathan; Arshad Ahmad; Mohamed Mahmoud Nasef; Universiti Teknologi Malaysia Campus, Kuala Lumpur

    2015-01-01

    Kinetic behaviour of graft copolymerisation of a nitrogenous heterocyclic monomer, 4-vinylpyridine (4-VP), onto electron beam irradiated poly(ethylene-co-tetrafluoroethylene) (ETFE) films was investigated in correlation with reaction parameters (absorbed dose, monomer concentration and reaction temperature). This was established by determination of initial polymerisation rate (r p0 ), characteristic radical recombination rate (γ) and delay time (t 0 ). The orders of the dependence of the initial rate of grafting on the absorbed dose and monomer concentration were found to be 2.28 and 3.49, respectively. The effect of temperature was investigated in the range of 50-70 deg C and the activation energy was determined. The incorporation of poly(4-VP) grafts and the accompanied chemical changes in the grafted ETFE films were monitored using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, respectively. The results of the present study showed that a quantitative kinetic description for grafting of 4-VP onto ETFE can be established and the degree of grafting can be tuned by controlling the reaction parameters. (author)

  9. Electrochemical oxidation of nitrogen-heterocyclic compounds at boron-doped diamond electrode.

    Xing, Xuan; Zhu, Xiuping; Li, Hongna; Jiang, Yi; Ni, Jinren

    2012-01-01

    Nitrogen-heterocyclic compounds (NHCs) are toxic and bio-refractory contaminants widely spread in environment. This study investigated electrochemical degradation of NHCs at boron-doped diamond (BDD) anode with particular attention to the effect of different number and position of nitrogen atoms in molecular structure. Five classical NHCs with similar structures including indole (ID), quinoline (QL), isoquinoline (IQL), benzotriazole (BT) and benzimidazole (BM) were selected as the target compounds. Results of bulk electrolysis showed that degradation of all NHCs was fit to a pseudo first-order equation. The five compounds were degraded with the following sequence: ID>QL>IQL>BT>BM in terms of their rates of oxidation. Quantum chemical calculation was combined with experimental results to describe the degradation character of NHCs at BDD anode. A linear relationship between degradation rate and delocalization energy was observed, which demonstrated that electronic charge was redistributed through the conjugation system and accumulated at the active sites under the attack of hydroxyl radicals produced at BDD anode. Moreover, atom charge was calculated by semi empirical PM3 method and active sites of NHCs were identified respectively. Analysis of intermediates by GC-MS showed agreement with calculation results. Copyright © 2011 Elsevier Ltd. All rights reserved.

  10. Two-photon fluorescence and fluorescence imaging of two styryl heterocyclic dyes combined with DNA.

    Gao, Chao; Liu, Shu-yao; Zhang, Xian; Liu, Ying-kai; Qiao, Cong-de; Liu, Zhao-e

    2016-03-05

    Two new styryl heterocyclic two-photon (TP) materials, 4-[4-(N-methyl)styrene]-imidazo [4,5-f][1,10] phenanthroline-benzene iodated salt (probe-1) and 4,4-[4-(N-methyl)styrene]-benzene iodated salt (probe-2) were successfully synthesized and studied as potential fluorescent probes of DNA detection. The linear and nonlinear photophysical properties of two compounds in different solvents were investigated. The absorption, one- and two-photon fluorescent spectra of the free dye and dye-DNA complex were also examined to evaluate their photophysical properties. The binding constants of dye-DNA were obtained according to Scatchard equation with good values. The results showed that two probes could be used as fluorescent DNA probes by two-photon excitation, and TP fluorescent properties of probe-1 are superior to that of probe-2. The fluorescent method date indicated that the mechanisms of dye-DNA complex interaction may be groove binding for probe-1 and electrostatic interaction for probe-2, respectively. The MTT assay experiments showed two probes are low toxicity. Moreover, the TP fluorescence imaging of DNA detection in living cells at 800 nm indicated that the ability to locate in cell nuclei of probe-1 is better than that of probe-2. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Metal and hydrogen catalysis in isotopic hydrogen exchange in some biologically important heterocyclic compounds

    Buncel, E.; Joly, H.A.; Jones, J.R.; Onyido, I.

    1989-01-01

    This study reports on the catalytic roles of metal and hydrogen ions in tritium exchange in some heterocyclic substrates which occur as residues in many biologically important molecules. We have found that detritiation of 1-methyl[2- 3 H]imidazole is inhibited by a number of metal ions. As well, inhibition of exchange rates was noted with Ag(I) and Cu(II) for [2- 3 H]thiazole and 1-methyl[8- 3 H]inosine, with Ag(I) for [2- 3 H]benzothiazole, and with Cu(II) for 1-methyl[8- 3 H]guanosine. A complete mechanistic description, which includes the various metal ion-coordinated species generated under the experimental conditions, is presented. The results demonstrate the reactivity order: protonated >> metal-coordinated >> neutral substrates. The differential catalytic effects of metal and hydrogen ions in these processes are discussed in terms of the extent of charge developed on the ligating heteroatom in the reaction intermediate. (author). 13 refs.; 1 fig

  12. Mechanism of Propylene Oxide Polymerization Promoted by N-Heterocyclic Olefins

    Al-Ghamdi, Miasser

    2017-01-11

    We report a mechanistic DFT investigation of the organopolymerization of propylene oxide (PO) promoted by N-heterocyclic olefins (NHOs) in combination with benzylic alcohol (BnOH). Calculations support the experimentally based hypothesis of two competing pathways, namely, the anionic and zwitterionic pathways. The former is based on an acid–base cooperativity between BnOH and the NHO, promoting ring opening of PO by BnO–. The latter occurs through the formation of a zwitterionic adduct by nucleophilic attack of the exocyclic carbon atom of the NHO on the PO, with the concerted ring opening of PO. The two initiating species cannot interconvert, and chain elongation can proceed from both initiation adducts. Potential energy surfaces were computed for a set of NHOs to clarify the effects of the steric and electronic properties of the NHO on the system reactivity. The results achieved represent useful insight toward the synthesis of PPO with better properties with respect to the polymer obtained with the experimental tested systems because the computationally proposed NHO system is the only one that favors the mechanism leading to higher molecular weight.

  13. Methods for estimating heterocyclic amine concentrations in cooked meats in the US diet.

    Keating, G A; Bogen, K T

    2001-01-01

    Heterocyclic amines (HAs) are formed in numerous cooked foods commonly consumed in the diet. A method was developed to estimate dietary HA levels using HA concentrations in experimentally cooked meats reported in the literature and meat consumption data obtained from a national dietary survey. Cooking variables (meat internal temperature and weight loss, surface temperature and time) were used to develop relationships for estimating total HA concentrations in six meat types. Concentrations of five individual HAs were estimated for specific meat type/cooking method combinations based on linear regression of total and individual HA values obtained from the literature. Using these relationships, total and individual HA concentrations were estimated for 21 meat type/cooking method combinations at four meat doneness levels. Reported consumption of the 21 meat type/cooking method combinations was obtained from a national dietary survey and the age-specific daily HA intake calculated using the estimated HA concentrations (ng/g) and reported meat intakes. Estimated mean daily total HA intakes for children (to age 15 years) and adults (30+ years) were 11 and 7.0 ng/kg/day, respectively, with 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) estimated to comprise approximately 65% of each intake. Pan-fried meats were the largest source of HA in the diet and chicken the largest source of HAs among the different meat types.

  14. Heterocyclic aromatic amines in domestically prepared chicken and fish from Singapore Chinese households.

    Salmon, C P; Knize, M G; Felton, J S; Zhao, B; Seow, A

    2006-04-01

    Chicken and fish samples prepared by 42 Singapore Chinese in their homes were obtained. Researchers were present to collect data on raw sample weight, cooking time, maximum cooking surface temperature, and cooked sample weight. Each participant prepared one pan-fried fish sample and two pan-fried chicken samples, one marinated, one not marinated. The cooked samples were analyzed for five heterocyclic aromatic amine (HAA) mutagens, including MeIQx (2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline); 4,8-DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline); 7,8-DiMeIQx (2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline); PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine), and IFP (2-amino-(1,6-dimethylfuro[3,2-e]imidazo[4,5-b])pyridine). A paired Student's t-test showed that marinated chicken had lower concentrations of PhIP (pchicken, and also that weight loss due to cooking was less in marinated chicken than in non-marinated chicken (pchicken (pchicken (pchicken (pchicken (pchicken (p<0.05). This study provides new information on HAA content in the Singapore Chinese diet.

  15. Synthesis, spectroscopic studies and reactivity of triphenylphosphine ruthenium (II) complexes with N-heterocyclic ligands

    Rivera, A.B.

    1989-01-01

    Reported is the chemistry of triphenylphosphine ruthenium (II) complexes of general formula RuCl 2 (PPh 3 ) 2 L 2 and RuCl 2 (PPh 3 ) 2 A, obtained from the reaction of RuCl 2 (PPh 3 ) 3 with N-heterocyclic ligands L, or A (of ambidentate nature). The electronic spectra exhibit two strong metal-to-ligand charge-transfer bands, ascribed to the b 1 (dxz)->b 1 (pi) and a 2 (dxy)->a 2 (pi) transitions, and a third, weak band ascribed to the b 2 (dyz)->a 2 (pi) transition. The electronic states and the vibrational modes of the complexes were characterized by means of their resonance Raman and infrared absorption spectra. Thermogravimetric and thermodifferential analysis indicated that the melting process is succeeded by an exothermic reaction, and that the weigh loss starts to occur only after this step. The complexes dissociated in CHCl 3 solution, showing preferential labilization of the phosphine ligands, as in the case of the hydrogenation catalyst Ru(PPh 3 ) 3 Cl 2 . In the presence of CO, RuCl 2 (CO) 2 L 2 complexes were gennerated. Several derivatives were isolated and characterized. (author) [pt

  16. Anti-trypanosomal activity of cationic N-heterocyclic carbene gold(I) complexes.

    Winter, Isabel; Lockhauserbäumer, Julia; Lallinger-Kube, Gertrud; Schobert, Rainer; Ersfeld, Klaus; Biersack, Bernhard

    2017-06-01

    Two gold(I) N-heterocyclic carbene complexes 1a and 1b were tested for their anti-trypanosomal activity against Trypanosoma brucei parasites. Both gold compounds exhibited excellent anti-trypanosomal activity (IC 50 =0.9-3.0nM). The effects of the gold complexes 1a and 1b on the T. b. brucei cytoskeleton were evaluated. Rapid detachment of the flagellum from the cell body occurred after treatment with the gold complexes. In addition, a quick and complete degeneration of the parasitic cytoskeleton was induced by the gold complexes, only the microtubules of the detached flagellum remained intact. Both gold compounds 1a and 1b feature selective anti-trypanosomal agents and were distinctly more active against T. b. brucei cells than against human HeLa cells. Thus, the gold complexes 1a and 1b feature promising drug candidates for the treatment of trypanosome infections such as sleeping sickness (human African Trypanosomiasis caused by Trypanosoma brucei parasites). Copyright © 2017 Elsevier B.V. All rights reserved.

  17. Evaluation of a new model system for studying the formation of heterocyclic amines.

    Messner, C; Murkovic, M

    2004-03-25

    Heterocyclic amines (HAs) are an important class of food mutagens and carcinogens, which can be found in cooked meat and fish. Increasing heating temperatures and times usually increase mutagenic activity in meat and meat extracts during cooking. We developed a model system, which allows to examine the effects of precursor composition and heating conditions (time and temperature) on the formation of HAs in meat. Homogenized and freeze dried meat samples (beef, pork chops, chicken breast and turkey breast) are heated with diethylene glycol in closed vials under stirring in a thermostated heating block. After an appropriate sample preparation (extraction and clean-up) ten different HAs were measured by HPLC analyses with gradient elution and mass selective detection. The time courses of HA-formation in the different kinds of meat at varying heating temperatures were determined up to heating times of 30 min. 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) was the most abundant HA in these experiments and reached the highest concentrations in the beef meat samples, as did the other HAs (MeIQ, AalphaC) at 220 degrees C in the heating block under stirred conditions. Additionally the influence of the antioxidant TBHQ (t-butylhydroquinone) on the formation of HAs in the model system was tested. However TBHQ effected only slight reductions of HA formation in all kinds of meat.

  18. Induction of micronuclei in V79 cells after combined treatments with heterocyclic aromatic amines.

    Perez, C; Lopez de Cerain, A; Bello, J

    2002-10-01

    Heterocyclic aromatic amines (HAs) appear in foods rich in proteins when subjected to different cooking processes. These amines have been demonstrated to be mutagenic in bacteria; in eucaryotic cells, controversial results have been referred. The objective of this study is to evaluate the clastogenic and/or aneugenic capacity of three HAs--2-amino-3-methylimidazo[4,5-f]quinoline (IQ), 2-amino-3-methylimidazo[4,5-f]quinoxaline (IQx), and 2-amino-3-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP)--in isolated as well as in combined treatments. The micronucleus test in vitro was used on V79 cells in the presence and absence of metabolic activation. The duration of the treatment was 2 h, and cytochalasin B was added for 21 h to stop cytokinesis; then, micronuclei (MN) were counted in binucleated cells. In the presence of metabolic activation, the three amines showed a significant increase in the number of MN with respect to the negative control. The PhIP amine presented the highest values and it also resulted slightly active in the absence of metabolic activation, although these differences have not been considered to be significant. The combined treatments of these amines have shown that the effects attributed to them when administered together are those that are expected for a possible additive effect; the effect attributed to each HA separately is not potentiated nor inhibited.

  19. Inhibitory effects of pomegranate seed extract on the formation of heterocyclic aromatic amines in beef and chicken meatballs after cooking by four different methods.

    Keşkekoğlu, Hasan; Uren, Ali

    2014-04-01

    Beef and chicken meatballs with a 0.5% (w/w) pomegranate seed extract were cooked using four different cooking methods (oven roasting, pan cooking, charcoal-barbecue, and deep-fat frying) and six heterocyclic aromatic amines; IQ, MeIQx, 4,8-DiMeIQx, PhIP, norharman, and harman were observed. In the beef meatballs, the highest inhibitory effects of pomegranate seed extract on heterocyclic aromatic amines formation were 68% for PhIP, 24% for norharman, 18% for harman, 45% for IQ, and 57% for MeIQx. Total heterocyclic aromatic amine formation was reduced by 39% and 46% in beef meatballs cooked by charcoal-barbecue and deep-fat frying, respectively. In the chicken meatballs, the highest inhibitory effects were 75% for PhIP, 57% for norharman, 28% for harman, 46% for IQ, and 49% for MeIQx. When the pomegranate seed extract was added to the chicken meatballs cooked by deep-fat frying, the total heterocyclic aromatic amine formation was inhibited by 49%, in contrast the total heterocyclic aromatic amine contents after oven roasting increased by 70%. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. La Convention de Rio sur la diversité biologique

    Maljean-Dubois , Sandrine

    2016-01-01

    International audience; Du 3 au 14 juin 1992, en écho à la première grande conférence onusienne sur l'environnement et le développement, celle de Stockholm organisée en 1972, se tenait à Rio de Janeiro la Conférence des Nations Unies sur l'environnement et le développement (CNUED), dite aussi Sommet de la Terre. Cette conférence marquait une étape dans la perception des enjeux environnementaux et suscitait de vifs espoirs. Un programme d'action pour le XXI ème siècle, Action 21, dont le chapi...