WorldWideScience

Sample records for benzyne-furan cycloadditions total

  1. Asymmetric total synthesis of (-)-lingzhiol via a Rh-catalysed [3+2] cycloaddition.

    Science.gov (United States)

    Long, Rong; Huang, Jun; Shao, Wenbin; Liu, Song; Lan, Yu; Gong, Jianxian; Yang, Zhen

    2014-01-01

    The development of efficient reactions for the one-pot construction of bicyclic ring systems bearing two quaternary carbon centres at their bridgehead positions represents a significant challenge to synthetic chemistry. The development of new methods capable of overcoming this challenge is highly desirable, because this motif can be found in a wide range of natural products with significant biological activities. Herein, we report an efficient [3+2] cycloaddition reaction between an enal and an alleno rhodium species, which was generated in situ from the corresponding enynol via a retro metal-propargylation reaction, to give [3.3.0] and [3.4.0] bicyclic systems bearing two quaternary atoms at their bridgehead positions. The developed chemistry has been successfully applied to the asymmetric total synthesis of natural product (-)-lingzhiol (4) for the first time in 17 steps. PMID:25483390

  2. Total Synthesis of (±)-Strychnine via a [4+2]-Cycloaddition/Rearrangement Cascade

    OpenAIRE

    Zhang, Hongjun; Boonsombat, Jutatip; Padwa, Albert

    2007-01-01

    A new strategy for the synthesis of the Strychnos alkaloid (±)-strychnine has been developed and is based on an intramolecular [4+2]-cycloaddition/rearrangement cascade of an indolyl substituted amidofuran. The critical D-ring was assembled by an intramolecular palladium catalyzed enolate-driven cross-coupling of an N-tethered vinyl iodide.

  3. Total synthesis of gracilioether F. Development and application of Lewis acid promoted ketene–alkene [2+2] cycloadditions and late-stage C—H oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Rasik, Christopher M. [Indiana Univ., Bloomington, IN (United States); Brown, M. Kevin [Indiana Univ., Bloomington, IN (United States)

    2014-12-22

    The first synthesis of gracilioether F, a polyketide natural product with an unusual tricyclic core and five contiguous stereocenters, is described. Key steps of the synthesis include a Lewis acid promoted ketene–alkene [2+2] cycloaddition and a late-stage carboxylic acid directed C(sp³)—H oxidation. The synthesis requires only eight steps from norbornadiene.

  4. Total Synthesis of Natural (–)- and ent-(+)-4-Desacetoxy-6,7-dihydrovindorosine and Natural and ent-Minovine: Oxadiazole Tandem Intramolecular Diels–Alder/1,3-Dipolar Cycloaddition Reaction

    OpenAIRE

    Yuan, ZhongQing; Ishikawa, Hayato; Boger, Dale L.

    2005-01-01

    Efficient and unusually concise total syntheses of both enantiomers of the Aspidosperma alkaloids 4-desacetoxy-6,7-dihydrovindorosine (12) and minovine (1) are detailed. A tandem intramolecular Diels–Alder/1,3-dipolar cycloaddition reaction of the 1,3,4-oxadiazole 8, in which three new rings, four new C–C bonds and five stereocenters are formed, is a key step in the sequence. The availability of optically active material permitted an assessment of the enantiomeric integrity of minovine and th...

  5. Asymmetric Organocatalytic Cycloadditions

    DEFF Research Database (Denmark)

    Mose, Rasmus

    2016-01-01

    were pioneered by Otto Paul Hermann Diels and Kurt Alder who discovered what later became known as the Diels Alder reaction. The Diels Alder reaction is a [4+2] cycloaddition in which a π4 component reacts with a π2 component via a cyclic transition state to generate a 6 membered ring. This reaction...... reactions constitute the first organocatalytic asymmetric higher order cycloadditions and a rational for the periselectivity and stereoselectivity is provided based on experimental and computational investigations....

  6. Cycloaddition Reactions of Deoxyribosylpropynoates

    Czech Academy of Sciences Publication Activity Database

    Hessler, F.; Kulhavá, L.; Císařová, I.; Otmar, Miroslav; Kotora, Martin

    2014-01-01

    Roč. 44, č. 9 (2014), s. 1232-1239. ISSN 0039-7911 Grant ostatní: AV ČR(CZ) IAA401110805 Institutional support: RVO:61388963 Keywords : Dewar benzenes * C-aryldeoxyribosides * unnatural nucleosides * cyclotrimerization * cycloaddition Subject RIV: CC - Organic Chemistry Impact factor: 0.929, year: 2014

  7. Cycloadditions in modern polymer chemistry.

    Science.gov (United States)

    Delaittre, Guillaume; Guimard, Nathalie K; Barner-Kowollik, Christopher

    2015-05-19

    Synthetic polymer chemistry has undergone two major developments in the last two decades. About 20 years ago, reversible-deactivation radical polymerization processes started to give access to a wide range of polymeric architectures made from an almost infinite reservoir of functional building blocks. A few years later, the concept of click chemistry revolutionized the way polymer chemists approached synthetic routes. Among the few reactions that could qualify as click, the copper-catalyzed azide-alkyne cycloaddition (CuAAC) initially stood out. Soon, many old and new reactions, including cycloadditions, would further enrich the synthetic macromolecular chemistry toolbox. Whether click or not, cycloadditions are in any case powerful tools for designing polymeric materials in a modular fashion, with a high level of functionality and, sometimes, responsiveness. Here, we wish to describe cycloaddition methodologies that have been reported in the last 10 years in the context of macromolecular engineering, with a focus on those developed in our laboratories. The overarching structure of this Account is based on the three most commonly encountered cycloaddition subclasses in organic and macromolecular chemistry: 1,3-dipolar cycloadditions, (hetero-)Diels-Alder cycloadditions ((H)DAC), and [2+2] cycloadditions. Our goal is to briefly describe the relevant reaction conditions, the advantages and disadvantages, and the realized polymer applications. Furthermore, the orthogonality of most of these reactions is highlighted because it has proven highly beneficial for generating unique, multifunctional polymers in a one-pot reaction. The overview on 1,3-dipolar cycloadditions is mostly centered on the application of CuAAC as the most travelled route, by far. Besides illustrating the capacity of CuAAC to generate complex polymeric architectures, alternative 1,3-dipolar cycloadditions operating without the need for a catalyst are described. In the area of (H)DA cycloadditions

  8. Synchronous intramolecular cycloadditions of the polyene macrolactam polyketide heronamide C.

    Science.gov (United States)

    Booth, Thomas J; Alt, Silke; Capon, Robert J; Wilkinson, Barrie

    2016-05-11

    A growing number of natural products appear to arise from biosynthetic pathways that involve pericyclic reactions. We show here that for the heronamides this can occur via two spontaneous pathways involving alternative thermal or photochemical intramolecular cycloadditions. PMID:27091090

  9. New Chromium Carbonyl Catalysts for [6+2] Cycloaddition Reactions

    OpenAIRE

    Kundig, Ernst Peter; Robvieux, Fabrice; Kondratenko, Mikhail

    2002-01-01

    The complexes, (benzene)chromiumdicarbonyl(methyl acrylate) and chromiumdicarbonylbis(cyclohexadiene), are precursors for the highly coordinatively unsaturated chromium dicarbonyl fragment 3, a catalyst for the cycloaddition of activated olefins to cycloheptatriene.

  10. Iridium-catalyzed intramolecular [4 + 2] cycloadditions of alkynyl halides

    OpenAIRE

    Andrew Tigchelaar; William Tam

    2012-01-01

    Iridium-catalyzed intramolecular [4 + 2] cycloadditions of diene-tethered alkynyl halides were investigated by using [IrCl(cod)]2 as catalyst, and dppe was found to be the most suitable phosphine ligand for the reaction. No oxidative insertion of the iridium into the carbon–halide bond was observed, and the reactions proceeded to provide the halogenated cycloadducts in good yield (75–94%). These results are the first examples of cycloadditions of alkynyl halides using an iridium c...

  11. Cycloadditions of Noncomplementary Substituted 1,2,3-Triazines

    OpenAIRE

    Anderson, Erin D.; Duerfeldt, Adam S.; Zhu, Kaicheng; Glinkerman, Christopher M.; Boger, Dale L.

    2014-01-01

    The scope of the [4 + 2] cycloaddition reactions of substituted 1,2,3-triazines, bearing noncomplementary substitution with electron-withdrawing groups at C4 and/or C6, is described. The studies define key electronic and steric effects of substituents impacting the reactivity, mode (C4/N1 vs C5/N2), and regioselectivity of the cycloaddition reactions of 1,2,3-triazines with amidines, enamines, and ynamines, providing access to highly functionalized heterocycles.

  12. Recent developments in gold-catalyzed cycloaddition reactions

    Directory of Open Access Journals (Sweden)

    Fernando López

    2011-08-01

    Full Text Available In the last years there have been extraordinary advances in the development of gold-catalyzed cycloaddition processes. In this review we will summarize some of the most remarkable examples, and present the mechanistic rational underlying the transformations.

  13. Photochemical Cycloadditions to 5,6-Dihydro-4-pyridones

    OpenAIRE

    Guerry, Philippe; Neier, Reinhard

    2007-01-01

    5,6-Dihydro-4-pyridones (3a-3c) undergo photochemical [2 + 2]-cycloaddition with olefins activated by an electron withdrawing group. Alkyi substituted double bonds could only be brought to react in the intramolecular cases 3d and 3e.

  14. Nitrogen heteroaromatic cations by [2+2+2] cycloaddition

    Czech Academy of Sciences Publication Activity Database

    Čížková, Martina; Kolivoška, Viliam; Císařová, I.; Šaman, David; Pospíšil, Lubomír; Teplý, Filip

    2011-01-01

    Roč. 9, č. 2 (2011), s. 450-462. ISSN 1477-0520 R&D Projects: GA ČR GA203/09/1614; GA ČR GA203/09/0705; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40400503 Keywords : modular synthesis * N-heteroaromatic cation * [2+2+2] cycloaddition Subject RIV: CC - Organic Chemistry Impact factor: 3.696, year: 2011

  15. Total synthesis of (±)-isophellibiline

    OpenAIRE

    Funk, Raymond L.; Belmar, Johannes

    2012-01-01

    The total synthesis of (±)-isophellibiline is described. This represents the first synthesis of a member of the nonaromatic homoerythrinan family of alkaloids. The tetracyclic ring system of the natural product was quickly assembled by a strategy that features a retrocycloaddition/cycloaddition reaction of an amidodioxin, an intramolecular Heck reaction and a 6π-electrocyclic ring closure of a dienoic acid.

  16. Total Synthesis of (-)-Daphenylline.

    Science.gov (United States)

    Yamada, Ryosuke; Adachi, Yohei; Yokoshima, Satoshi; Fukuyama, Tohru

    2016-05-10

    Total synthesis of (-)-daphenylline, a hexacyclic Daphniphyllum alkaloid, was achieved. Construction of the tricyclic DEF ring system was initiated by asymmetric Negishi coupling followed by an intramolecular Friedel-Crafts reaction. Installation of a side chain onto the tricyclic core was carried out through Sonogashira coupling, stereocontrolled Claisen rearrangement by taking advantage of the characteristic conformation of the tricyclic DEF core, and the stereoselective alkylation of a lactone. After the introduction of a glycine unit, the ABC ring system was stereoselectively constructed through intramolecular cycloaddition of the cyclic azomethine ylide. PMID:27062676

  17. Isocyanide based [4+1] cycloaddition reactions: an indispensable tool in multi-component reactions (MCRs).

    Science.gov (United States)

    Kaur, Tanpreet; Wadhwa, Preeti; Bagchi, Sourav; Sharma, Anuj

    2016-05-19

    The advent of cycloaddition reactions in the synthesis of heterocycles and their ever burgeoning applications in the fields of material chemistry, catalysis and drugs have been a profound scientific development. In particular, isocyanide based cycloaddition reactions have been harbingers of an exciting new chapter in the realms of organic synthesis. The emergence of numerous synthetic protocols utilizing formal cycloaddition of isocyanides with conjugated heterodienes has unleashed countless opportunities to design and synthesize diverse heterocyclic scaffolds. To date, there has not been any exclusive review on a formal [4+1] cycloaddition involving isocyanides. The present review highlights the journey of formal [4+1] cycloaddition reactions of isocyanides with diverse electrophilic substrates viz. oxadienes, azadienes, thioacyl imines, alkylidene amides, alkylidene hydrazines, α,β-unsaturated nitro compounds, α-thioxothioamides, nitroso alkenes, acyl imines, vinyl ketenes, vinyl isocyanates, etc. to afford functionalized pyrroles, imidazoles, furans, oxazoles, pyrazoles, etc. PMID:27063921

  18. 1,3-Dipolar cycloaddition reactivities of perfluorinated aryl azides with enamines and strained dipolarophiles.

    Science.gov (United States)

    Xie, Sheng; Lopez, Steven A; Ramström, Olof; Yan, Mingdi; Houk, K N

    2015-03-01

    The reactivities of enamines and predistorted (strained) dipolarophiles toward perfluoroaryl azides (PFAAs) were explored experimentally and computationally. Kinetic analyses indicate that PFAAs undergo (3 + 2) cycloadditions with enamines up to 4 orders of magnitude faster than phenyl azide reacts with these dipolarophiles. DFT calculations were used to identify the origin of this rate acceleration. Orbital interactions between the cycloaddends are larger due to the relatively low-lying LUMO of PFAAs. The triazolines resulting from PFAA-enamine cycloadditions rearrange to amidines at room temperature, while (3 + 2) cycloadditions of enamines and phenyl azide yield stable, isolable triazolines. The 1,3-dipolar cycloadditions of norbornene and DIBAC also show increased reactivity toward PFAAs over phenyl azide but are slower than enamine-azide cycloadditions. PMID:25553488

  19. Synthesis of Spiroisoxazolines by 1,3-Dipolar Cycloaddition

    OpenAIRE

    Peter Ertl; Vladimír Ondrus; Lubor Fisera; Peter Micuch

    1997-01-01

    The cycloaddition of the chiral nitrile oxide 1 to 1-R-substituted 3,3-methylene-5,5-dimethyl-2-pyrrolidinones 2 (where R is H, n-butyl-, 1,1-dimethylethoxycarbonyl-, 1-methylethenyl- and acetyl-) proceeds regioselectively under the formation of spiroisoxazolines, namely 7-R-substituted-6-oxo-8,8-dimethyl-1-oxa-2,7-diazaspiro[4,4]non-2-enes 5 and 6. The asymmetric induction expected by the a-chiral centre of the nitrile oxide 1 was not very effective, diastereoisomers 5 and 6 were formed in a...

  20. A surprising dipolar cycloaddition provides ready access to aminoglycosides.

    Science.gov (United States)

    Dahl, Russell S; Finney, Nathaniel S

    2004-07-14

    This contribution describes the results of a new research effort in our laboratory aimed at the synthesis of novel aminoglycosides and amino-C-glycosides. Despite the importance of such compounds, and the previous development of some methodological solutions, this remains an important area of research. Notable features of our approach, which is distinct from and complementary to previous efforts, are the following: (1) Reliance on a surprising and unprecedented formation of glycal triazolines via an inverse electron demand dipolar cycloaddition of glucal. We believe this desirable transformation has not previously been discovered because of the unusual selection of substrates and solvent required. (2) Very mild reaction conditions. An initial thermal cycloaddition is carried out in an inert solvent, the triazoline generated is photochemically converted to a reactive aziridine, and the crude aziridine undergoes ring opening at room temperature in the presence of a nucleophile and a mild Lewis acid catalyst. (3) Formation of products lacking an N-acyl group, allowing ready synthesis of novel glucosamine derivatives. PMID:15237974

  1. Preparation of dispersible graphene through organic functionalization of graphene using a zwitterion intermediate cycloaddition approach

    NARCIS (Netherlands)

    Zhang, Xiaoyan; Browne, Wesley R.; Feringa, Ben L.

    2012-01-01

    Highly functionalized graphene were obtained through a zwitterion intermediate cycloaddition onto exfoliated graphene flakes under new reaction conditions. The functionalized graphene obtained formed stable dispersions in common solvents, including dimethylformamide (DMF), CHCl3 and water. Its dispe

  2. Ni-Catalyzed Ketene Cycloaddition: A System that Resists the Formation of Decarbonylation Side Products

    OpenAIRE

    Kumar, Puneet; Troast, Dawn M.; Cella, Rodrigo; Louie, Janis

    2011-01-01

    Ni-phosphine complexes were used as catalysts for the cycloaddition of various ketenes and diynes. In general, 2,4-cyclohexadieonones were formed instead of products arising from decarbonylation of the ketenes.

  3. Polar [3 + 2] cycloaddition of ketones with electrophilically activated carbonyl ylides. Synthesis of spirocyclic dioxolane indolinones.

    Science.gov (United States)

    Bentabed-Ababsa, Ghenia; Derdour, Aicha; Roisnel, Thierry; Sáez, Jose A; Domingo, Luis R; Mongin, Florence

    2008-09-01

    The [3 + 2] cycloaddition reaction between carbonyl ylides generated from epoxides and ketones (ethyl pyruvate, ethyl phenylglyoxylate, isatin, N-methylisatin and 5-chloroisatin) to give substituted dioxolanes and spirocyclic dioxolane indolinones was investigated. The effect of microwave irradiation on the outcome of the reaction was studied. The thermal reaction between 2,2-dicyano-3-phenyloxirane and N-methylisatin was theoretically studied using DFT methods. This reaction is a domino process that comprises two steps. The first is the thermal ring opening of the epoxide to yield a carbonyl ylide intermediate, whereas the second step is a polar [3 + 2] cycloaddition to yield the final spiro cycloadducts. The cycloaddition presents a low stereoselectivity and a large regio- and chemoselectivity. Analysis of the electrophilicity values and the Fukui functions of the reagents involved in the cycloaddition step allowed the chemical outcome to be explained. PMID:18698474

  4. Solvent-free one-pot 1,3-dipolar cycloaddition reactions of dihydropyran derived nitrone

    Indian Academy of Sciences (India)

    Bhaskar Chakraborty; Prawin Kumar Sharma; Neelam Rai; Chiran Devi Sharma

    2012-05-01

    Microwave-induced 1,3-dipolar cycloaddition reactions of dihydropyran derived nitrone with various activated alkenes have been studied in situ and found to afford new isoxazolidine derivatives with moderate selectivity.

  5. Computational study of a model system of enzyme-mediated [4+2] cycloaddition reaction.

    Directory of Open Access Journals (Sweden)

    Evgeniy G Gordeev

    Full Text Available A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reaction was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X and semiempirical levels (PM6-DH2, PM6 performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modeling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation.

  6. Computational study of a model system of enzyme-mediated [4+2] cycloaddition reaction.

    Science.gov (United States)

    Gordeev, Evgeniy G; Ananikov, Valentine P

    2015-01-01

    A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reaction was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X) and semiempirical levels (PM6-DH2, PM6) performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the present study it was demonstrated that the [4+2] cycloaddition reaction may benefit from moving along the energetically balanced reaction coordinate, which enabled the catalytic rate enhancement of the [4+2] cycloaddition pathway involving a single transition state. Modeling of such a system with coordination of three amino acids indicated a reliable decrease of activation energy by ~18.0 kcal/mol as compared to a non-catalytic transformation. PMID:25853669

  7. Catalytic Enantioselective 1,3-Dipolar Cycloadditions of Azomethine Ylides for Biology-Oriented Synthesis

    OpenAIRE

    Narayan, Rishikesh; Potowski, Marco; Jia, Zhi-Jun; Antonchick, Andrey P.; Waldmann, Herbert

    2014-01-01

    Conspectus Cycloaddition reactions are among the most powerful methods for the synthesis of complex compounds. In particular, the development and application of the 1,3-dipolar cycloaddition, an important member of this reaction class, has grown immensely due to its powerful ability to efficiently build various five-membered heterocycles. Azomethine ylides are commonly used as dipoles for the synthesis of the pyrrolidine scaffold, which is an important motif in natural products, pharmaceutica...

  8. [2+2+2] cycloaddition reactions involving allenes catalysed by rhodium

    OpenAIRE

    Haraburda, Ewelina

    2015-01-01

    The development of new chemical processes for the formation of carbon-carbon bonds is an important topic in organic chemistry. In particular, the transition metal catalysed [2+2+2] cycloaddition reaction is a highly efficient synthetic tool that allows six-membered polysubstituted carbo- and heterocyclic derivatives to be obtained in an atom economy process. Allenes are versatile substrates for cycloaddition reactions that provide a good reactivity profile together with the ability to increas...

  9. Covalent functionalization by cycloaddition reactions of pristine, defect-free graphene

    OpenAIRE

    Daukiya, L.; Mattioli, C.; Aubel, D.; Hajjar-Garreau, S.; Vonau, F.; Denys, E.; Reiter, G.; J. Fransson; E. Perrin; Bocquet, M-L.; Bena, C.; A. Gourdon; Simon, L.

    2016-01-01

    Based on a low temperature scanning tunneling microscopy study, we present a direct visualization of a cycloaddition reaction performed for some specific fluorinated maleimide molecules deposited on graphene. These studies showed that the cycloaddition reactions can be carried out on the basal plane of graphene, even when there are no pre-existing defects. In the course of covalently grafting the molecules to graphene, the sp2 conjugation of carbon atoms was broken and local sp3 bonds were cr...

  10. An Unprecedented Formal [5 + 2] Cycloaddition of Nitrones with o-Carboryne via Tandem [3 + 2] Cycloaddition/Oxygen Migration/Aromatization Sequence.

    Science.gov (United States)

    Zhao, Da; Zhang, Jiji; Xie, Zuowei

    2015-11-01

    Heterocyclic skeletons are widespread among natural products as well as bioactive molecules. Cycloaddition reaction has created new opportunities to access heterocycles of great complexity due to its advantage of multiple bond formation in a single step. Here, we describe an unprecedented formal [5 + 2] cycloaddition of nitrone with o-carboryne to afford carborane-fused seven-membered heterocycles. Experimental and theoretical data suggest that a sequence of [3 + 2] cycloaddition, N-O bond cleavage, oxygen migration and rearomatization is involved in this unprecedented reaction. In this process, the nitrone moieties serve as five-atom coupling partners with both heteroatoms being incorporated into the framework of the final products. This new methodology also offers new insight into the chemistry of nitrones. PMID:26467943

  11. Catalytic enantioselective 1,3-dipolar cycloadditions of azomethine ylides for biology-oriented synthesis.

    Science.gov (United States)

    Narayan, Rishikesh; Potowski, Marco; Jia, Zhi-Jun; Antonchick, Andrey P; Waldmann, Herbert

    2014-04-15

    Cycloaddition reactions are among the most powerful methods for the synthesis of complex compounds. In particular, the development and application of the 1,3-dipolar cycloaddition, an important member of this reaction class, has grown immensely due to its powerful ability to efficiently build various five-membered heterocycles. Azomethine ylides are commonly used as dipoles for the synthesis of the pyrrolidine scaffold, which is an important motif in natural products, pharmaceuticals, and biological probes. The reaction between azomethine ylides and cyclic dipolarophiles allows access to polycyclic products with considerable complexity. The extensive application of the 1,3-dipolar cycloaddition is based on the fact that the desired products can be obtained with high yield in a regio- and stereocontrolled manner. The most attractive feature of the 1,3-dipolar cycloaddition of azomethine ylides is the possibility to generate pyrrolidines with multiple stereocenters in a single step. The development of enantioselective cycloadditions became a subject of intensive and impressive studies in recent years. Among many modes of stereoinduction, the application of chiral metal-ligand complexes has emerged as the most viable option for control of enantioselectivity. In chemical biology research based on the principle of biology-oriented synthesis (BIOS), compound collections are prepared inspired by natural product scaffolds. In BIOS, biological relevance is employed as the key criterion to generate hypotheses for the design and synthesis of focused compound libraries. In particular, the underlying scaffolds of natural product classes provide inspiration for BIOS because they define the areas of chemical space explored by nature, and therefore, they can be regarded as "privileged". The scaffolds of natural products are frequently complex and rich in stereocenters, which necessitates the development of efficient enantioselective methodologies. This Account highlights examples

  12. Total synthesis of atropurpuran.

    Science.gov (United States)

    Gong, Jing; Chen, Huan; Liu, Xiao-Yu; Wang, Zhi-Xiu; Nie, Wei; Qin, Yong

    2016-01-01

    Due to their architectural intricacy and biological significance, the synthesis of polycyclic diterpenes and their biogenetically related alkaloids have been the subject of considerable interest over the last few decades, with progress including the impressive synthesis of several elusive targets. Despite tremendous efforts, conquering the unique structural types of this large natural product family remains a long-term challenge. The arcutane diterpenes and related alkaloids, bearing a congested tetracyclo[5.3.3.0(4,9).0(4,12)]tridecane unit, are included in these unsolved enigmas. Here we report a concise approach to the construction of the core structure of these molecules and the first total synthesis of (±)-atropurpuran. Pivotal features of the synthesis include an oxidative dearomatization/intramolecular Diels-Alder cycloaddition cascade, sequential aldol and ketyl-olefin cyclizations to assemble the highly caged framework, and a chemoselective and stereoselective reduction to install the requisite allylic hydroxyl group in the target molecule. PMID:27387707

  13. Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

    KAUST Repository

    Lamberti, Marina

    2012-01-23

    The performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azidealkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr 3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2- iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide. © 2012 American Chemical Society.

  14. Dimerization of propargyl and homopropargyl 6-azido-6-deoxy-glycosides upon 1,3-dipolar cycloaddition

    Directory of Open Access Journals (Sweden)

    2008-08-01

    Full Text Available Copper-catalyzed, thermal or microwave promoted 1,3-dipolar cycloaddition (Click Reaction of 2-propynyl and 3-butynyl 2,3,4-tri-O-acetyl-6-azido-6-deoxy-glycopyranosides in the D-gluco, D-galacto and D-manno series afford the corresponding dimeric cycloaddition products.

  15. Citrus Peel Additives for One-Pot Triazole Formation by Decarboxylation, Nucleophilic Substitution, and Azide-Alkyne Cycloaddition Reactions

    Science.gov (United States)

    Mendes, Desiree E.; Schoffstall, Allen M.

    2011-01-01

    This undergraduate organic laboratory experiment consists of three different reactions occurring in the same flask: a cycloaddition reaction, preceded by decarboxylation and nucleophilic substitution reactions. The decarboxylation and cycloaddition reactions occur using identical Cu(I) catalyst and conditions. Orange, lemon, and other citrus fruit…

  16. Dimerization of propargyl and homopropargyl 6-azido-6-deoxy-glycosides upon 1,3-dipolar cycloaddition

    OpenAIRE

    Pietrzik, Nikolas; Schmollinger, Daniel; Ziegler, Thomas

    2008-01-01

    Copper-catalyzed, thermal or microwave promoted 1,3-dipolar cycloaddition (Click Reaction) of 2-propynyl and 3-butynyl 2,3,4-tri-O-acetyl-6-azido-6-deoxy-glycopyranosides in the D-gluco, D-galacto and D-manno series afford the corresponding dimeric cycloaddition products.

  17. Advances in nickel-catalyzed cycloaddition reactions to construct carbocycles and heterocycles.

    Science.gov (United States)

    Thakur, Ashish; Louie, Janis

    2015-08-18

    Transition-metal catalysis has revolutionized the field of organic synthesis by facilitating the construction of complex organic molecules in a highly efficient manner. Although these catalysts are typically based on precious metals, researchers have made great strides in discovering new base metal catalysts over the past decade. This Account describes our efforts in this area and details the development of versatile Ni complexes that catalyze a variety of cycloaddition reactions to afford interesting carbocycles and heterocycles. First, we describe our early work in investigating the efficacy of N-heterocyclic carbene (NHC) ligands in Ni-catalyzed cycloaddition reactions with carbon dioxide and isocyanate. The use of sterically hindered, electron donating NHC ligands in these reactions significantly improved the substrate scope as well as reaction conditions in the syntheses of a variety of pyrones and pyridones. The high reactivity and versatility of these unique Ni(NHC) catalytic systems allowed us to develop unprecedented Ni-catalyzed cycloadditions that were unexplored due to the inefficacy of early Ni catalysts to promote hetero-oxidative coupling steps. We describe the development and mechanistic analysis of Ni/NHC catalysts that couple diynes and nitriles to form pyridines. Kinetic studies and stoichiometric reactions confirmed a hetero-oxidative coupling pathway associated with this Ni-catalyzed cycloaddition. We then describe a series of new substrates for Ni-catalyzed cycloaddition reactions such as vinylcyclopropanes, aldehydes, ketones, tropones, 3-azetidinones, and 3-oxetanones. In reactions with vinycyclopropanes and tropones, DFT calculations reveal noteworthy mechanistic steps such as a C-C σ-bond activation and an 8π-insertion of vinylcyclopropane and tropone, respectively. Similarly, the cycloaddition of 3-azetidinones and 3-oxetanones also requires Ni-catalyzed C-C σ-bond activation to form N- and O-containing heterocycles. PMID:26200651

  18. Application of Cycloaddition Reactions to the Syntheses of Novel Boron Compounds

    Directory of Open Access Journals (Sweden)

    John A. Maguire

    2010-12-01

    Full Text Available This review covers the application of cycloaddition reactions in forming the boron-containing compounds such as symmetric star-shaped boron-enriched dendritic molecules, nano-structured boron materials and aromatic boronic esters. The resulting boron compounds are potentially important reagents for both materials science and medical applications such as in boron neutron capture therapy (BNCT in cancer treatment and as drug delivery agents and synthetic intermediates for carbon-carbon cross-coupling reactions. In addition, the use of boron cage compounds in a number of cycloaddition reactions to synthesize unique aromatic species will be reviewed briefly.

  19. Computational Study of a Model System of Enzyme-Mediated [4+2] Cycloaddition Reaction

    OpenAIRE

    Gordeev, Evgeniy G.; Ananikov, Valentine P.

    2015-01-01

    A possible mechanistic pathway related to an enzyme-catalyzed [4+2] cycloaddition reac-tion was studied by theoretical calculations at density functional (B3LYP, O3LYP, M062X) and semiempirical levels (PM6-DH2, PM6) performed on a model system. The calculations were carried out for the key [4+2] cycloaddition step considering enzyme-catalyzed biosynthesis of Spinosyn A in a model reaction, where a reliable example of a biological Diels-Alder reaction was reported experimentally. In the presen...

  20. Synthesis of Macrocyclic Tetrazoles for Rapid Photoinduced Bioorthogonal 1,3-Dipolar Cycloaddition Reactions

    OpenAIRE

    Yu, Zhipeng; Lim, Reyna K. V.; Lin, Qing

    2010-01-01

    A series of conformationally constrained, macrocyclic tetrazoles were expediently prepared by double alkylation of a bis(o-phenolyl)tetrazole precursor. Several of them showed excellent reactivity toward norbornene in a photoinduced tetrazole-alkene cycloaddition reaction in organic solvent as well as toward a norbornene-modified protein in PBS buffer.

  1. One-Pot Functionalization of Graphene with Porphyrin through Cycloaddition Reactions

    NARCIS (Netherlands)

    Zhang, Xiaoyan; Hou, Lili; Cnossen, Arjen; Coleman, Anthony C.; Ivashenko, Oleksii; Rudolf, Petra; Wees, Bart J. van; Browne, Wesley R.; Feringa, Ben L.

    2011-01-01

    Two types of graphene-based hybrid materials, graphene-TPP (TPP=tetraphenylporphyrin) and graphene-PdTPP (PdTPP=palladium tetraphenylporphyrin), were prepared directly from pristine graphene through one-pot cycloaddition reactions. The hybrid materials were characterized by thermogravimetric analysi

  2. 3+2-Dipolar cycloaddition of dianhydrohexitol azidoderivatives with N-arylmaleimides

    Science.gov (United States)

    Gella, I. M.; Babak, N. L.; Drushlyak, T. G.; Shishkina, S. V.; Musatov, V. I.; Lipson, V. V.

    2015-11-01

    Dianhydrohexitol azides dipolar 3+2 cycloaddition with N-arylmaleimides has been studied with NMR (1H and 13C, COSY, NOESY and HSQC) and X-ray analysis. In spite of low asymmetrical induction in this reaction, diastereomerically pure products have been obtained. These products are interesting over their structural similarity to griseolic acid derivatives and dihydropyrrolotriazoles, significant for pharmaceutics.

  3. Copper on Chitosan: A Recyclable Heterogeneous Catalyst for Azide-alkyne Cycloaddition Reactions in Water

    Science.gov (United States)

    Copper sulfate is immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with copper sulfate; the ensuing catalyst has been utilized for the azide-alkyne cycloaddition in aqueous media and it can be recycled and reused many time without loosing it...

  4. Totalsynthese von (±)-Codein durch 1,3-dipolare Cycloaddition

    OpenAIRE

    Erhard, Thomas

    2011-01-01

    Die Nitron-Cycloaddition an ein dearomatisiertes Phenol ermöglichte den leichten Aufbau des Phenanthrengerüstes von Codein in der gewünschten Konfiguration. Weitere Schritte führten mit kompletter Diastereoselektivität zu Allopseudocodein und nach Allylverschiebung durch Hydrolyse der Chlorcodide schließlich zu (±)-Codein.

  5. Cycloaddition-Rearrangement Sequence of 2-Amido Substituted Furans as a Method of Synthesizing Hexahydroindolinones.

    Science.gov (United States)

    Padwa, Albert; Brodney, Michael A.; Satake, Kyosuke; Straub, Christopher S.

    1999-06-25

    A convenient synthesis of various substituted hexahydroindolinones has been achieved by an intramolecular Diels-Alder cycloaddition (IMDAF) reaction of 2-amido substituted furans. The initially formed [4 + 2] cycloadduct undergoes nitrogen-assisted ring opening followed by deprotonation of the resulting zwitterion to give the rearranged ketone. The stereochemical outcome of the IMDAF cycloaddition has the sidearm of the tethered alkenyl group oriented syn with respect to the oxygen bridge. The reaction rate and product yield were found to be markedly dependent upon the electronic properties of the alkenyl pi-bond. 2-[2-(tert-Butoxycarbonylfuran-2-yl-amino)ethyl]acrylic acid methyl ester was synthesized from 3-chlorocarbonyl-but-3-enoic acid methyl ester. Thermolysis of the carbomethoxy activated furanamide occurred at 80 degrees C to produce a rearranged hexahydroindolinone. When Me(3)Al or (MeO)(3)Al was used as a Lewis acid to promote the cycloaddition, a rearranged alcohol was obtained. The initially formed [4 + 2] cycloadduct undergoes ring opening in the presence of the Lewis acid, and the resulting aluminum intermediate delivers the substituent group from the same face as the neighboring oxygen to ultimately furnish a rearranged cis-alcohol. In contrast to this result, a mixture of diastereomeric methoxy alcohols was isolated when the IMDAF cycloaddition was carried out in methanol. The major isomer corresponds to the trans-diastereomer that results from trapping of the iminium ion from the less crowded face of the pi-bond. PMID:11674531

  6. Cycloadditions to Epoxides Catalyzed by GroupIII-V Transition-Metal Complexes

    KAUST Repository

    D'Elia, Valerio

    2015-05-25

    Complexes of groupIII-V transition metals are gaining increasing importance as Lewis acid catalysts for the cycloaddition of dipolarophiles to epoxides. This review examines the latest reports, including homogeneous and heterogeneous applications. The pivotal step for the cycloaddition reactions is the ring opening of the epoxide following activation by the Lewis acid. Two modes of cleavage (C-C versus C-O) have been identified depending primarily on the substitution pattern of the epoxide, with lesser influence observed from the Lewis acid employed. The widely studied cycloaddition of CO2 to epoxides to afford cyclic carbonates (C-O bond cleavage) has been scrutinized in terms of catalytic efficiency and reaction mechanism, showing that unsophisticated complexes of groupIII-V transition metals are excellent molecular catalysts. These metals have been incorporated, as well, in highly performing, recyclable heterogeneous catalysts. Cycloadditions to epoxides with other dipolarophiles (alkynes, imines, indoles) have been conducted with scandium triflate with remarkable performances (C-C bond cleavage). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A Palladium-Catalyzed Vinylcyclopropane (3 + 2) Cycloaddition Approach to the Melodinus Alkaloids

    KAUST Repository

    Goldberg, Alexander F. G.

    2011-08-19

    A palladium-catalyzed (3+2) cycloaddition of a vinylcyclopropane and a β-nitrostyrene is employed to rapidly assemble the cyclopentane core of the Melodinus alkaloids. The ABCD ring system of the natural product family is prepared in six steps from commercially available materials.

  8. Asymmeric Formal [3+3]-Cycloaddition Reactions of Nitrones with Electrophilic Vinylcarbene Intermediates

    OpenAIRE

    Wang, Xiaochen; Xu, Xinfang; Zavalij, Peter Y.; Doyle, Michael P.

    2011-01-01

    With metal carbene access to dipolar intermediates, 3,6-dihydro-1,2-oxazines are produced in high yields by dirhodium(II) carboxylate catalyzed reactions between nitrones and a β-TBSO-substituted vinyldiazoacetate. High enantiocontrol occurs with catalysis by N-phthaloyl-(S)-(amino acid)-ligated dirhodium carboxylates for [3+3]-cycloaddition reactions with both acyclic and cyclic nitrones.

  9. Synthesis of functionalized polyesters by the "click" copper-catalyzed alkyne-azide cycloaddition

    OpenAIRE

    Lecomte, Philippe; Riva, Raphaël; Jérôme, Christine

    2009-01-01

    The functionalization of aliphatic polyesters by the copper-mediated azide–alkyne Huisgen’s cycloaddition is very efficient under mild conditions, which prevents degradation from occurring. The implementation of this reaction requires the synthesis of aliphatic polyesters bearing pendant alkynes and azides, which can be carried out either by polycondensation or by ring-opening polymerization.

  10. Preparation of dispersible graphene through organic functionalization of graphene using a zwitterion intermediate cycloaddition approach

    OpenAIRE

    Zhang, Xiaoyan; Browne, Wesley R.; Feringa, Ben L.

    2012-01-01

    Highly functionalized graphene were obtained through a zwitterion intermediate cycloaddition onto exfoliated graphene flakes under new reaction conditions. The functionalized graphene obtained formed stable dispersions in common solvents, including dimethylformamide (DMF), CHCl3 and water. Its dispersion in water is especially useful in a wide range of areas, such as composites, devices and biological applications.

  11. Rhodium-Catalyzed Linear Codimerization and Cycloaddition of Ketenes with Alkynes

    OpenAIRE

    Teruyuki Kondo; Masatsugu Niimi; Yuki Yoshida; Kenji Wada; Take-aki Mitsudo; Yu Kimura; Akio Toshimitsu

    2010-01-01

    A novel rhodium-catalyzed linear codimerization of alkyl phenyl ketenes with internal alkynes to dienones and a novel synthesis of furans by an unusual cycloaddition of diaryl ketenes with internal alkynes have been developed. These reactions proceed smoothly with the same rhodium catalyst, RhCl(PPh3)3, and are highly dependent on the structure and reactivity of the starting ketenes.

  12. Catalytic asymmetric exo-selective [6+3] cycloaddition of iminoesters with fulvenes.

    Science.gov (United States)

    Potowski, Marco; Antonchick, Andrey P; Waldmann, Herbert

    2013-09-14

    A novel exo-selective [6+3] cycloaddition approach for the highly enantioselective synthesis of polysubstituted piperidines was developed. The developed methodology was applied in a one-pot [6+3]-[4+2] dicycloaddition, allowing the construction of structurally and stereochemically rich polycyclic compounds from simple building blocks. PMID:23884088

  13. Organometallic additions in tandem with radical and cycloaddition reactions - methodology and applications

    Czech Academy of Sciences Publication Activity Database

    Kapras, Vojtěch; Hernandez Guerra, Daniel; Just, David; Řehová, Lucie; Jahn, Ullrich

    Praha: Czech Chemical Society, 2015. s. 33. [Liblice 2015. Advances in Organic, Bioorganic and Pharmaceutical Chemistry /50./. 06.11.2015-08.11.2015, Olomouc] R&D Projects: GA ČR GAP207/11/1598; GA ČR GA13-40188S Institutional support: RVO:61388963 Keywords : organometallic additions * cycloaddition reactions Subject RIV: CC - Organic Chemistry

  14. Rh-catalysed [5 + 1] cycloaddition of allenylcyclopropanes and CO: reaction development and application to the formal synthesis of (-)-galanthamine.

    Science.gov (United States)

    Liu, Cheng-Hang; Yu, Zhi-Xiang

    2016-07-01

    A Rh-catalysed [5 + 1] cycloaddition of allenylcyclopropanes and CO has been developed to synthesize functionalized 2-methylidene-3,4-cyclohexenones. The scope of this methodology has been investigated, showing that various functional groups can be tolerated. Both di- and tri-substituted allenylcyclopropanes can be applied to this cycloaddition and the [5 + 1] cycloadducts with the E configuration were obtained as the major products. In addition, the present [5 + 1] cycloaddition reaction has been utilized as a key step in the formal synthesis of the natural product (-)-galanthamine. PMID:27253492

  15. Cascade Reaction of Donor-Acceptor Cyclopropanes: Mechanistic Studies on Cycloadditions with Nitrosoarenes and cis-Diazenes.

    Science.gov (United States)

    Chidley, Tristan; Vemula, Naresh; Carson, Cheryl A; Kerr, Michael A; Pagenkopf, Brian L

    2016-06-17

    Tandem ring opening, elimination, and cycloaddition of donor-acceptor cyclopropanes were observed in Yb(OTf)3-catalyzed cycloaddition with nitrosoarenes. The reaction results in formation of tetrahydro-1,2-oxazine instead of the normal cycloadduct isoxazolidine via in situ nitrone formation. A similar cascade sequence was observed with cis-diazines. Mechanistic studies on this unique transformation offer an entirely new approach for reaction design with donor-acceptor cyclopropanes. PMID:27267360

  16. 1,3-Dipolar Cycloadditions of Benzonitrile Oxide with Various Dipolarophiles in Aqueous Solutions. A Kinetic Study

    OpenAIRE

    Mersbergen, Dick van; Wijnen, Jan W.; Engberts, Jan B. F. N.

    1998-01-01

    The second-order rate constants for the 1,3-dipolar cycloaddition of benzonitrile oxide (1) with various dipolarophiles (2a-e) were determined in aqueous media and in organic solvents to gain more insight into the influence of an aqueous medium on pericyclic reactions. 1,3-Dipolar cycloadditions with electron-poor dipolarophiles are accelerated in water and protic solvents, whereas an aqueous medium has no special effect when electron-poor dipolarophiles are involved. These observations can b...

  17. "Click" Chemistry: Application of Copper Metal in Cu-Catalyzed Azomethine Imine-Alkyne Cycloadditions.

    Science.gov (United States)

    Pušavec Kirar, Eva; Grošelj, Uroš; Mirri, Giorgio; Požgan, Franc; Strle, Gregor; Štefane, Bogdan; Jovanovski, Vasko; Svete, Jurij

    2016-07-15

    A series of 16 copper-catalyzed azomethine imine-alkyne cycloaddition (CuAIAC) reactions between four pyrazolidinone-1-azomethine imines and four terminal ynones gave the corresponding fluorescent cycloadducts as bimane analogues in very high yields. The applicability of CuAIAC was demonstrated by the fluorescent labeling of functionalized polystyrene and by using Cu-C and Cu-Fe as catalysts. Experimental evidence, kinetic measurements, and correlation between a clean catalyst surface and the reaction rate are in agreement with a homotopic catalytic system with catalytic Cu(I)-acetylide formed from Cu(0) by "in situ" oxidation. The availability of azomethine imines, mild reaction conditions, simple workup, and scalability make CuAIAC a viable supplement to the Cu-catalyzed azide-alkyne cycloaddition reaction in "click" chemistry. PMID:27305104

  18. Investigation of the Pyridinium Ylide—Alkyne Cycloaddition as a Fluorogenic Coupling Reaction

    Directory of Open Access Journals (Sweden)

    Simon Bonte

    2016-03-01

    Full Text Available The cycloaddition of pyridinium ylides with alkynes was investigated under mild conditions. A series of 13 pyridinium salts was prepared by alkylation of 4-substituted pyridines. Their reactivity with propiolic ester or amide in various reaction conditions (different temperatures, solvents, added bases was studied, and 11 indolizines, with three points of structural variation, were, thus, isolated and characterized. The highest yields were obtained when electron-withdrawing groups were present on both the pyridinium ylide, generated in situ from the corresponding pyridinium salt, and the alkyne (X, Z = ester, amide, CN, carbonyl, etc.. Electron-withdrawing substituents, lowering the acid dissociation constant (pKa of the pyridinium salts, allow the cycloaddition to proceed at pH 7.5 in aqueous buffers at room temperature.

  19. Dynamically Complex [6+4] and [4+2] Cycloadditions in the Biosynthesis of Spinosyn A.

    Science.gov (United States)

    Patel, Ashay; Chen, Zhuo; Yang, Zhongyue; Gutiérrez, Osvaldo; Liu, Hung-Wen; Houk, K N; Singleton, Daniel A

    2016-03-23

    SpnF, an enzyme involved in the biosynthesis of spinosyn A, catalyzes a transannular Diels-Alder reaction. Quantum mechanical computations and dynamic simulations now show that this cycloaddition is not well described as either a concerted or stepwise process, and dynamical effects influence the identity and timing of bond formation. The transition state for the reaction is ambimodal and leads directly to both the observed Diels-Alder and an unobserved [6+4] cycloadduct. The potential energy surface bifurcates and the cycloadditions occur by dynamically stepwise modes featuring an "entropic intermediate". A rapid Cope rearrangement converts the [6+4] adduct into the observed [4+2] adduct. Control of nonstatistical dynamical effects may serve as another way by which enzymes control reactions. PMID:26909570

  20. Photo- and radiation chemical cycloaddition of maleic acid derivatives to ethylene and acetylene under elavated pressure

    International Nuclear Information System (INIS)

    Based on spectroscopic and kinetic measurements the influence of high pressure on some selected photochemical cycloaddition-reactions is studied. The photo-cycloaddition-reaction of maleic acid anhydride with ethylen has been performed under high ethylen pressures ( 90%). Surprisingly the quantum yield of the cyclo aduct decreases with increasing ethylene pressure from PHI = 0.06 at p = 1 bar to PHI = 0.022 at p = 42 bar. Based on Stern-Volmer quenching experiments, the decrease in ring formation with increasing ethylene concentrations could be explained by an endoergic triplet energy transfer from maleic acid anhydride to ethylene. The type II dissociation of butyrophenone has been quenched also with ethylene. With a lifetime for the first excited butyrophenone triplett state of tau = 6.8 x 10-8 sec, obtained from kinetic data, the velocity constant can be calculated for this reaction with the result k5 = 3 x 106 M-1sec-1. (orig./HK)

  1. Rhodium-catalyzed acyloxy migration of propargylic esters in cycloadditions, inspiration from the recent "gold rush".

    Science.gov (United States)

    Shu, Xing-Zhong; Shu, Dongxu; Schienebeck, Casi M; Tang, Weiping

    2012-12-01

    Transition metal-catalyzed acyloxy migration of propargylic esters offers versatile entries to allene and vinyl carbene intermediates for various fascinating subsequent transformations. Most π-acidic metals (e.g. gold and platinum) are capable of facilitating these acyloxy migration events. However, very few of these processes involve redox chemistry, which are well-known for most other transition metals such as rhodium. The coupling of acyloxy migration of propargylic esters with oxidative addition, migratory insertion, and reductive elimination may lead to ample new opportunities for the design of new reactions. This tutorial review summarizes recent developments in Rh-catalyzed 1,3- and 1,2-acyloxy migration of propargylic esters in a number of cycloaddition reactions. Related Au- and Pt-catalyzed cycloadditions involving acyloxy migration are also discussed. PMID:22895533

  2. Catalyst free visible light induced cycloaddition as an avenue for polymer ligation.

    Science.gov (United States)

    Lederhose, Paul; Wüst, Kilian N R; Barner-Kowollik, Christopher; Blinco, James P

    2016-05-21

    The current study introduces a tetrazole species able to perform a rapid, visible light induced nitrile imine-mediated tetrazole-ene cycloaddition (NITEC). Full conversion of the tetrazole species under mild, catalyst free conditions is reported. Importantly, the visible light ligation technology is applied as a method for the modification and ligation of polymers featuring the rapid, clean and exclusive formation of the desired cycloadduct. PMID:27004740

  3. Polar [3 + 2] cycloaddition of ketones with electrophilically activated carbonyl ylides. Synthesis of spirocyclic dioxolane indolinones.

    OpenAIRE

    Bentabed-Ababsa, Ghenia; Derdour, Aicha; Roisnel, Thierry; Sáez, Jose A.; Luis R. Domingo; Mongin, Florence

    2008-01-01

    The [3 + 2] cycloaddition reaction between carbonyl ylides generated from epoxides and ketones (ethyl pyruvate, ethyl phenylglyoxylate, isatin, N-methylisatin and 5-chloroisatin) to give substituted dioxolanes and spirocyclic dioxolane indolinones was investigated. The effect of microwave irradiation on the outcome of the reaction was studied. The thermal reaction between 2,2-dicyano-3-phenyloxirane and N-methylisatin was theoretically studied using DFT methods. This reaction is a domino proc...

  4. Cycloaddition Reactions of C,N-Diphenylnitrone to Methylene-γ-butyrolactones

    Directory of Open Access Journals (Sweden)

    Andrea Goti

    2000-04-01

    Full Text Available Cycloaddition of C,N-diphenylnitrone to α-methylene-γ-butyrolactone afforded two diastereomeric 5-spirosubstituted isoxazolidines with high selectivity. Structural assignment was ascertained by NMR studies and an X-ray diffraction experiment on a single crystal of the major isomer and the diastereoselectivity was rationalized on examination of the alternative transition states leading to the two diastereoisomers.

  5. Cycloaddition Reactions of C,N-Diphenylnitrone to Methylene-γ-butyrolactones

    OpenAIRE

    Andrea Goti; Cristina Faggi; Cordero, Franca M.; Martina Cacciarini

    2000-01-01

    Cycloaddition of C,N-diphenylnitrone to α-methylene-γ-butyrolactone afforded two diastereomeric 5-spirosubstituted isoxazolidines with high selectivity. Structural assignment was ascertained by NMR studies and an X-ray diffraction experiment on a single crystal of the major isomer and the diastereoselectivity was rationalized on examination of the alternative transition states leading to the two diastereoisomers.

  6. Functionalization of Graphene with Nitrile Groups by Cycloaddition of Tetracyanoethylene Oxide

    OpenAIRE

    Xiaojun Peng; Yang Li; Guoliang Zhang; Fengbao Zhang; Xiaobin Fan

    2013-01-01

    Graphene has got considerable attention in both experimental and theoretical fields for its extraordinary properties. Covalent functionalization is an efficient strategy to render graphene additional properties and overcome its shortcomings such as zero band gap and nondispersibility in solvents. This study reports the synthesis and characterizations of a new kind of functionalized graphene, graphene-TCNEO, obtained by 1,3-dipolar cycloaddition. The graphene-TCNEO was systematically character...

  7. Rhodium(I) catalyzed [2+2+2] cycloaddition reactions: experimental and theoretical studies

    OpenAIRE

    Dachs Soler, Anna

    2011-01-01

    The [2+2+2] cycloaddition reaction involves the formation of three carbon-carbon bonds in one single step using alkynes, alkenes, nitriles, carbonyls and other unsaturated reagents as reactants. This is one of the most elegant methods for the construction of polycyclic aromatic compounds and heteroaromatic, which have important academic and industrial uses. The thesis is divided into ten chapters including six related publications. The first study based on the Wilkinson’s catalyst, RhCl(PPh3)...

  8. Chiral Phosphoric Acid-Catalyzed Enantioselective Formal [3+2] Cycloaddition of Azomethine Imines with Enecarbamates.

    Science.gov (United States)

    Wang, Yang; Wang, Qian; Zhu, Jieping

    2016-06-01

    The first catalytic asymmetric inverse electron demand 1,3-dipolar cycloaddition of azomethine imines with enecarbamates has been developed. Isoquinoline-fused pyrazolidines containing two or three contiguous stereogenic centers were obtained in high yields with excellent regio-, diastereo-, and enantioselectivities. The pyrazolidine ring can be opened to install an aminal, α-amino nitrile, or homoallylamine function with an excellent control of the newly generated stereogenic center. Access to aminobenzo[a]quinolizidine is also documented. PMID:27135440

  9. Rapid Metal -free Macromolecular Coupling via in situ Nitrile Oxide-Activated Alkene Cycloaddition

    OpenAIRE

    Isaacman, Michael J.; Cui, Weibin; Theogarajan, Luke S.

    2014-01-01

    Nitrile oxide 1,3 dipolar cycloaddition is a simple and powerful coupling methodology. However, the self-dimerization of nitrile oxides has prevented the widespread use of this strategy for macromolecular coupling. By combining an in situ nitrile oxide generation with a highly reactive activated dipolarophile, we have overcome these obstacles and present a metal-free macromolecular coupling strategy for the modular synthesis of several ABA triblock copolymers. Nitrile oxides were generated in...

  10. 1,3-Dipolar Cycloaddition Reactions of Substituted Benzyl Azides with Acetylenic Compounds

    Directory of Open Access Journals (Sweden)

    Sultan T. Abu-Orabi

    2002-02-01

    Full Text Available We review in this article some of our work which has been published over the last fifteen years in the area of 1,3-dipolar cycloaddition reactions of substituted benzyl azides with acetylenic compounds to form the corresponding 1,2-3-triazoles. Several triazole derivatives were transformed into triazolopyridazine and triazolo-1,3,4-oxadiazole derivatives upon their reactions with hydrazine.

  11. SYNTHESIS AND CHARACTERIZATION OF TRIAZOLE CONTAINING LIQUID CRYSTALLINE POLYMERS THROUGH 1,3-DIPOLAR CYCLOADDITION POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Devamani; Srividhya; Sundaram; Manjunathan; Sivashankaran; Nithyanandan; Subramanan; Balamurugan; Sengodan; Senthil

    2009-01-01

    Liquid crystalline polymers containing 1,2,3-triazole units as linking groups have been synthesized from the monomers containing triad ester diazide and flexible dialkyne ester by 1,3-cycloaddition reaction and were characterized. Click reaction of azide and alkyne functionals catalyzed by Cu(I) yielded target polyesters with 1,2,3-triazole groups.The structure of the polymer was confirmed by spectral techniques.GPC analysis reveals that the polymers have moderate molecular weight with narrow distributio...

  12. Application of Cycloaddition Reactions to the Syntheses of Novel Boron Compounds

    OpenAIRE

    John A. Maguire; Hosmane, Narayan S; Yinghuai Zhu; Xiao Siwei

    2010-01-01

    This review covers the application of cycloaddition reactions in forming the boron-containing compounds such as symmetric star-shaped boron-enriched dendritic molecules, nano-structured boron materials and aromatic boronic esters. The resulting boron compounds are potentially important reagents for both materials science and medical applications such as in boron neutron capture therapy (BNCT) in cancer treatment and as drug delivery agents and synthetic intermediates for carbon-carbon cross-c...

  13. Metal-free intermolecular formal cycloadditions enable an orthogonal access to nitrogen heterocycles

    Science.gov (United States)

    Xie, Lan-Gui; Niyomchon, Supaporn; Mota, Antonio J.; González, Leticia; Maulide, Nuno

    2016-01-01

    Nitrogen-containing heteroaromatic cores are ubiquitous building blocks in organic chemistry. Herein, we present a family of metal-free intermolecular formal cycloaddition reactions that enable highly selective and orthogonal access to isoquinolines and pyrimidines at will. Applications of the products are complemented by a density functional theory mechanistic analysis that pinpoints the crucial factors responsible for the selectivity observed, including stoichiometry and the nature of the heteroalkyne. PMID:26975182

  14. NMR studies on 1,3-dipolar cycloaddition of nitrile oxides to norbornenes

    Energy Technology Data Exchange (ETDEWEB)

    Gucma, Miroslaw; Golebiewski, W. Marek; Krawczyk, Maria, E-mail: golebiewski@ipo.waw.pl [Institute of Industrial Organic Chemistry, Warsaw (Poland)

    2013-05-15

    The 1,3-dipolar cycloaddition reaction of nitrile oxides to norbornenes substituted with an acrylate-derived moiety was examined. Only adducts to norbornene system were formed with a good exo selectivity and complete site-selectivity. Structures of the products were elucidated by an extensive application of electrospray ionization-mass spectrometry (ESI-MS) and 2D {sup 1}H and {sup 13}C nuclear magnetic resonance (NMR). (author)

  15. Easy access to heterobimetallic complexes for medical imaging applications via microwave-enhanced cycloaddition

    OpenAIRE

    Nicolas Desbois; Sandrine Pacquelet; Adrien Dubois; Clément Michelin; Claude P. Gros

    2015-01-01

    The Cu(I)-catalysed Huisgen cycloaddition, known as “click” reaction, has been applied to the synthesis of a range of triazole-linked porphyrin/corrole to DOTA/NOTA derivatives. Microwave irradiation significantly accelerates the reaction. The synthesis of heterobimetallic complexes was easily achieved in up to 60% isolated yield. Heterobimetallic complexes were easily prepared as potential MRI/PET (SPECT) bimodal contrast agents incorporating one metal (Mn, Gd) for the enhancement of contras...

  16. A facile regioselective synthesis of novel spiroacenaphthene pyrroloisoquinolines through 1,3-dipolar cycloaddition reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sarrafi, Yaghoub; Asghari, Asieh; Sadatshahabi, Marzieh, E-mail: ysarrafi@umz.ac.ir [Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran (Iran, Islamic Republic of); Hamzehloueian, Mahshid [Department of Chemistry, Jouybar Branch, Islamic Azad University, Jouybar (Iran, Islamic Republic of); Alimohammadi, Kamal [Department of Chemistry, Dr. Shariati Branch, University of Farhangian, Sari (Iran, Islamic Republic of)

    2013-12-01

    An efficient one-pot three-component procedure for the synthesis of novel spiroacenaphthene pyrroloisoquinolines with high regioselectivity is described. These compounds were prepared from 1,3-dipolar cycloaddition of an azomethine ylide generated from acenaphthenequinone and 1,2,3,4-tetrahydroisoquinoline via [1,5]-H shift, with chalcone and nitrostyrene derivatives as dipolarophiles. The structure and stereochemistry of the cycloadducts have been established by single crystal X-ray structure and spectroscopic techniques. (author)

  17. 1,3-Dipolar Cycloaddition Reactivities of Perfluorinated Aryl Azides with Enamines and Strained Dipolarophiles

    OpenAIRE

    Xie, Sheng; Lopez, Steven A.; Ramström, Olof; Yan, Mingdi; Houk, K. N.

    2015-01-01

    The reactivities of enamines and predistorted (strained) dipolarophiles toward perfluoroaryl azides (PFAAs) were explored experimentally and computationally. Kinetic analyses indicate that PFAAs undergo (3 + 2) cycloadditions with enamines up to 4 orders of magnitude faster than phenyl azide reacts with these dipolarophiles. DFT calculations were used to identify the origin of this rate acceleration. Orbital interactions between the cycloaddends are larger due to the relatively low-lying LUMO...

  18. Quantumchemical study of the [2+3] cycloaddition of nitroethene with (Z)-C,N-diphenylnitrone

    OpenAIRE

    Jasi?ski, Radomir; Jasi?ska, Ewa; Mikulska, Maria

    2011-01-01

    Global and local reactivity indexes indicate polar character of the [2+3] cycloaddition of nitroethene to (Z)-C,Ndiphenylnitrone. The regioselectivity of these reaction is determined by the attack of oxygen-centered nucleophilic site of the nitrone on b-carbon atom in nitroethene. This is confirmed by B3LYP/6-31G(d) simulations of the reaction pathways.

  19. Bridged 2,2'-biazole derivatives by 1,3-dipolar cycloaddition

    OpenAIRE

    Pablo, María S. de; Gandasegui Rodríguez, María Teresa; Vaquero López, Juan José; García Navío, José Luis; Álvarez-Builla Gómez, Julio

    1992-01-01

    Azomethine ylides derived from 3,4-dihydropyrrolo[1,2-a]pyrazinium salts undergo 1,3-dipolar cycloaddition reactions to yield 5,6-dihydrodipyrrolo[1,2-a:2',1'-c]-pyrazine and 5,6-dihydroimidazo[1,2-a]-pyrrolo[2,1-c]pyrazin-4-inium-2-olate and 2-thiolate derivatives. S-Methylation followed by nucleophilic displacement of methylthio group convened the 2-thiolate derivatives into new conjugated betaines.

  20. Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions

    OpenAIRE

    Wilson Silva do Nascimento; Mauro Gomes da Silva; Ronaldo Nascimento de Oliveira; Celso Amorim Câmara

    2010-01-01

    Naphthoquinones are known according to their important bio-activities, such as their antitumoral and topoisomerase inhibition properties. From 2-azido (3) or 2,3-diacetylene-1,4-naphthoquinone (4) it was possible to obtain triazole derivatives (naphthoquinonic). This work describes the synthesis of two novel molecules, with triazole groups linked to 1,4-naphthoquinone using the 1,3-dipolar cycloaddition and Sonogashira reactions. The synthetic strategy followed two routes (Scheme 1). First, w...

  1. Strain-Promoted 1,3-Dipolar Cycloaddition of Cycloalkynes and Organic Azides.

    Science.gov (United States)

    Dommerholt, Jan; Rutjes, Floris P J T; van Delft, Floris L

    2016-04-01

    A nearly forgotten reaction discovered more than 60 years ago-the cycloaddition of a cyclic alkyne and an organic azide, leading to an aromatic triazole-enjoys a remarkable popularity. Originally discovered out of pure chemical curiosity, and dusted off early this century as an efficient and clean bioconjugation tool, the usefulness of cyclooctyne-azide cycloaddition is now adopted in a wide range of fields of chemical science and beyond. Its ease of operation, broad solvent compatibility, 100 % atom efficiency, and the high stability of the resulting triazole product, just to name a few aspects, have catapulted this so-called strain-promoted azide-alkyne cycloaddition (SPAAC) right into the top-shelf of the toolbox of chemical biologists, material scientists, biotechnologists, medicinal chemists, and more. In this chapter, a brief historic overview of cycloalkynes is provided first, along with the main synthetic strategies to prepare cycloalkynes and their chemical reactivities. Core aspects of the strain-promoted reaction of cycloalkynes with azides are covered, as well as tools to achieve further reaction acceleration by means of modulation of cycloalkyne structure, nature of azide, and choice of solvent. PMID:27573141

  2. Theoretical study on the mechanism of cycloaddition between dimethyl methylene carbene and acetone

    Institute of Scientific and Technical Information of China (English)

    LU Xiuhui; WU Weirong; YU Haibin; XU Yuehua

    2005-01-01

    The mechanism of the cycloaddition reaction of singlet dimethyl methylene carbene and acetone has been studied by using second-order Moller-Plesset perturbation and density functional theory. The geometrical parameters, harmonic vibrational frequencies and energy of stationary points on the potential energy surface are calculated by MP2/6-31G* and B3LYP/6-31G* methods. The results show that path b of the cycloaddition reaction (1) would be the major reactive channel of the cycloaddition reaction between singlet dimethyl methylene carbene and acetone, which proceeds in two steps: i) The two reactants form an energy-rich intermediate (INT1b), which is an exothermic reaction of 23.3 kJ/mol with no energy barrier. ii) The intermediate INT1b isomerizes to a three-membered ring product (P1) via transition state TS1b with energy barrier of 22.2 kJ/mol. The reaction rate of this reaction and its competitive reactions do greatly differ, with excellent selectivity. In view of dynamics and thermodynamics, this reaction is suitable for occurring at 1 atm and temperature range of 300―800 K, in which the reaction will have not only the larger spontaneous tendency and equilibrium constant but also the faster reaction rate.

  3. Theory of the formation and decomposition of N-heterocyclic aminooxycarbenes through metal-assisted [2+3]-dipolar cycloaddition/retro-cycloaddition.

    Science.gov (United States)

    Novikov, Alexander S; Kuznetsov, Maxim L; Pombeiro, Armando J L

    2013-02-18

    The theoretical background of the formation of N-heterocyclic oxadiazoline carbenes through a metal-assisted [2+3]-dipolar cycloaddition (CA) reaction of nitrones R(1)CH=N(R(2))O to isocyanides C≡NR and the decomposition of these carbenes to imines R(1)CH=NR(2) and isocyanates O=C=NR is discussed. Furthermore, the reaction mechanisms and factors that govern these processes are analyzed in detail. In the absence of a metal, oxadiazoline carbenes should not be accessible due to the high activation energy of their formation and their low thermodynamic stability. The most efficient promotors that could assist the synthesis of these species should be "carbenophilic" metals that form a strong bond with the oxadiazoline heterocycle, but without significant involvement of π-back donation, namely, Au(I), Au(III), Pt(II), Pt(IV), Re(V), and Pd(II) metal centers. These metals, on the one hand, significantly facilitate the coupling of nitrones with isocyanides and, on the other hand, stabilize the derived carbene heterocycles toward decomposition. The energy of the LUMO(CNR) and the charge on the N atom of the C≡N group are principal factors that control the cycloaddition of nitrones to isocyanides. The alkyl-substituted nitrones and isocyanides are predicted to be more active in the CA reaction than the aryl-substituted species, and the N,N,C-alkyloxadiazolines are more stable toward decomposition relative to the aryl derivatives. PMID:23296691

  4. Hetero [6+3] cycloaddition of fulvenes with N-alkylidene glycine esters: a facile synthesis of the delavayine and incarvillateine framework.

    Science.gov (United States)

    Hong, Bor-Cherng; Gupta, Arun Kumar; Wu, Ming-Fun; Liao, Ju-Hsiou; Lee, Gene-Hsiang

    2003-05-15

    [reaction: see text] In contrast to the [3+2] or [4+3] cycloaddition of N-metalated azomethine ylides and various alkenes, N-benzylidene glycine ethyl ester reacts with fulvenes to give the hetero [6+3] cycloaddition adducts with high stereoselectivity, constituting an efficient and novel route to [2]pyrindines. PMID:12735753

  5. Design of Redox/Radical Sensing Molecules via Nitrile Imine-Mediated Tetrazole-ene Cycloaddition (NITEC).

    Science.gov (United States)

    Lederhose, Paul; Haworth, Naomi L; Thomas, Komba; Bottle, Steven E; Coote, Michelle L; Barner-Kowollik, Christopher; Blinco, James P

    2015-08-21

    The current study introduces a novel synthetic avenue for the preparation of profluorescent nitroxides via nitrile imine-mediated tetrazole-ene cycloaddition (NITEC). The photoinduced cycloaddition was performed under metal-free, mild conditions allowing the preparation of a library of the nitroxide functionalized pyrazolines and corresponding methoxyamines. High reaction rates and full conversion were observed, with the presence of the nitroxide having no significant impact on the cycloaddition performance. The formed products were investigated with respect to their photophysical properties in order to quantify their "switch on/off" behavior. The fluorescence quenching performance is strongly dependent on the distance between the chromophore and the free radical spin as demonstrated theoretically and experimentally. Highest levels of fluorescence quenching were achieved for pyrazolines with the nitroxide directly fused to the chromophore. Importantly, the pyrazoline profluorescent nitroxides were shown to efficiently act as sensors for redox/radical processes. PMID:26168007

  6. Density Functional Study on [3+2]-Dipolar Cycloaddition Reaction of the N-heterocyclic Carbene Boryl Azide with Olefins

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xinghui; Wang, Ketai; Niu, Teng; Li, Shanshan [Lanzhou Univ. of Arts and Science, Lanzhou (Korea, Republic of)

    2014-05-15

    The cycloaddition reactions of the N-heterocyclic carbene boryl azide with methyl acrylate, butenone, and hexafluoropropene have been investigated theoretically. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum model (PCM) for the solvent (C6H6). The title reaction could produce 4- and 5-substituted 1,2,3-triazolines, respectively. The reaction systems have the higher chemical reactivity with the low barriers and could be favored. Yet the smaller differences have been found to occur in energetics, and the cycloaddition reactions occur for s-trans conformations over s-cis conformations. The calculations indicated that the cycloaddition reaction of the alkenes have certain regioselectivity.

  7. Density Functional Study on [3+2]-Dipolar Cycloaddition Reaction of the N-heterocyclic Carbene Boryl Azide with Olefins

    International Nuclear Information System (INIS)

    The cycloaddition reactions of the N-heterocyclic carbene boryl azide with methyl acrylate, butenone, and hexafluoropropene have been investigated theoretically. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum model (PCM) for the solvent (C6H6). The title reaction could produce 4- and 5-substituted 1,2,3-triazolines, respectively. The reaction systems have the higher chemical reactivity with the low barriers and could be favored. Yet the smaller differences have been found to occur in energetics, and the cycloaddition reactions occur for s-trans conformations over s-cis conformations. The calculations indicated that the cycloaddition reaction of the alkenes have certain regioselectivity

  8. Triazol-substituted titanocenes by strain-driven 1,3-dipolar cycloadditions

    Directory of Open Access Journals (Sweden)

    Andreas Gansäuer

    2014-07-01

    Full Text Available An operationally simple, convenient, and mild strategy for the synthesis of triazole-substituted titanocenes via strain-driven 1,3-dipolar cycloadditions between azide-functionalized titanocenes and cyclooctyne has been developed. It features the first synthesis of titanocenes containing azide groups. These compounds constitute ‘second-generation’ functionalized titanocene building blocks for further synthetic elaboration. Our synthesis is modular and large numbers of the complexes can in principle be prepared in short periods of time. Some of the triazole-substituted titanocenes display high cyctotoxic activity against BJAB cells. Comparison of the most active complexes allows the identification of structural features essential for biological activity.

  9. Polymer immobilized Cu(I) formation and azide-alkyne cycloaddition: A one pot reaction

    OpenAIRE

    Islam, Rafique Ul; Taher, Abu; Choudhary, Meenakshi; Siwal, Samarjeet; Mallick, Kaushik

    2015-01-01

    During the polymerization of aniline using copper sulphate, act as an oxidizing agent, the in-situ synthesized Cu(I) ion catalyzed the cyclo-addition between azides and alkynes. This work represents the merging of two steps, synthesis of the catalyst and application of the catalyst, in a one pot reaction. The elimination of the separate catalyst synthesis step is economic in terms of cost and time. As aniline was used as one of the reactant components so there is no requirement to use additio...

  10. Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

    OpenAIRE

    Regina Berg; Straub, Bernd F.

    2013-01-01

    The copper-catalyzed azide–alkyne cycloaddition (CuAAC) is one of the most broadly applicable and easy-to-handle reactions in the arsenal of organic chemistry. However, the mechanistic understanding of this reaction has lagged behind the plethora of its applications for a long time. As reagent mixtures of copper salts and additives are commonly used in CuAAC reactions, the structure of the catalytically active species itself has remained subject to speculation, which can be attributed to the ...

  11. Catalytic aerobic oxidation and tandem enantioselective cycloaddition in cascade multicomponent synthesis.

    Science.gov (United States)

    Potowski, Marco; Merten, Christian; Antonchick, Andrey P; Waldmann, Herbert

    2015-03-23

    An efficient multicomponent cascade transformation for the highly diastereo- and enantioselective synthesis of complex natural product inspired polycyclic products from simple starting materials is described. The cascade is initiated by copper-catalyzed aerobic CH oxidation of cyclopentadiene to cyclopentadienone followed by double catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides. The cascade synthesis efficiently yields structurally complex 5,5,5-tricyclic products with eight stereocenters with good yields and excellent diastereo- and enantiocontrol using one catalyst. PMID:25676025

  12. Synthesis and 1,3-Dipolar Cycloaddition Reactions of Chiral Maleimides

    Directory of Open Access Journals (Sweden)

    Lubor Fisera

    1997-02-01

    Full Text Available New routes to the synthesis of various novel chiral maleimides are described. The oxabicyclic anhydride 2 readily available exo-Diels-Alder adduct of furan and maleic anhydride was used as a vehicle, which in turn reacted with hydrochlorides of amino acids 3a-f in the presence of Et3N with release of furan to give the requisite novel chiral imides 4a-f in good to moderate yields. The stereoselectivity of 1,3-dipolar cycloaddition of nitrile oxides with prepared chiral imides 4a-f is investigated.

  13. Azide-Alkyne Huisgen [3+2] Cycloaddition Using CuO Nanoparticles

    OpenAIRE

    Hyunjoon Song; Byeong-Su Kim; Sungkyun Park; Ji Chan Park; Seongwan Jang; Aram Kim; Hyuntae Kang; Hyunje Woo; Kang Hyun Park

    2012-01-01

    Recent developments in the synthesis of CuO nanoparticles (NPs) and their application to the [3+2] cycloaddition of azides with terminal alkynes are reviewed. With respect to the importance of click chemistry, CuO hollow NPs, CuO hollow NPs on acetylene black, water-soluble double-hydrophilic block copolymer (DHBC) nanoreactors and ZnO–CuO hybrid NPs were synthesized. Non-conventional energy sources such as microwaves and ultrasound were also applied to these click reactions, and good catalyt...

  14. Easy access to heterobimetallic complexes for medical imaging applications via microwave-enhanced cycloaddition.

    Science.gov (United States)

    Desbois, Nicolas; Pacquelet, Sandrine; Dubois, Adrien; Michelin, Clément; Gros, Claude P

    2015-01-01

    The Cu(I)-catalysed Huisgen cycloaddition, known as "click" reaction, has been applied to the synthesis of a range of triazole-linked porphyrin/corrole to DOTA/NOTA derivatives. Microwave irradiation significantly accelerates the reaction. The synthesis of heterobimetallic complexes was easily achieved in up to 60% isolated yield. Heterobimetallic complexes were easily prepared as potential MRI/PET (SPECT) bimodal contrast agents incorporating one metal (Mn, Gd) for the enhancement of contrast for MRI applications and one "cold" metal (Cu, Ga, In) for future radionuclear imaging applications. Preliminary relaxivity measurements showed that the reported complexes are promising contrast agents (CA) in MRI. PMID:26664643

  15. Easy access to heterobimetallic complexes for medical imaging applications via microwave-enhanced cycloaddition

    Directory of Open Access Journals (Sweden)

    Nicolas Desbois

    2015-11-01

    Full Text Available The Cu(I-catalysed Huisgen cycloaddition, known as “click” reaction, has been applied to the synthesis of a range of triazole-linked porphyrin/corrole to DOTA/NOTA derivatives. Microwave irradiation significantly accelerates the reaction. The synthesis of heterobimetallic complexes was easily achieved in up to 60% isolated yield. Heterobimetallic complexes were easily prepared as potential MRI/PET (SPECT bimodal contrast agents incorporating one metal (Mn, Gd for the enhancement of contrast for MRI applications and one “cold” metal (Cu, Ga, In for future radionuclear imaging applications. Preliminary relaxivity measurements showed that the reported complexes are promising contrast agents (CA in MRI.

  16. The structure of SpnF, a standalone enzyme that catalyzes [4 + 2] cycloaddition.

    Science.gov (United States)

    Fage, Christopher D; Isiorho, Eta A; Liu, Yungnan; Wagner, Drew T; Liu, Hung-wen; Keatinge-Clay, Adrian T

    2015-04-01

    In the biosynthetic pathway of the spinosyn insecticides, the tailoring enzyme SpnF performs a [4 + 2] cycloaddition on a 22-membered macrolactone to forge an embedded cyclohexene ring. To learn more about this reaction, which could potentially proceed through a Diels-Alder mechanism, we determined the 1.50-Å-resolution crystal structure of SpnF bound to S-adenosylhomocysteine. This sets the stage for advanced experimental and computational studies to determine the precise mechanism of SpnF-mediated cyclization. PMID:25730549

  17. 1,3-Dipolare Cycloaddition von N2O an hochreaktive Mehrfachbindungen

    OpenAIRE

    Plefka, Oliver

    2011-01-01

    In der vorliegenden Arbeit wird über 1,3-dipolare Cycloadditionen mit Lachgas (N2O) unter milden Reaktionstemperaturen (≈ RT) berichtet. N2O ist ein sehr unreaktives 1,3-dipolares Reagenz. Bisher in der Literatur durchgeführte 1,3-dipolare Cycloadditionen mit N2O benötigten immer sehr drastische und gefährliche Reaktionsbedingungen (bis zu 300°C und 500 atm.). Dabei entstanden nach einer (postulierten) einleitenden 1,3-dipolaren Cycloaddition von N2O an Olefine oder Alkine immer nur sticks...

  18. Straightforward Synthesis of Dihydrobenzo[a]fluorenes through Au(I)-Catalyzed Formal [3 + 3] Cycloadditions

    OpenAIRE

    García García, Patricia; Rashid, Muhammad A.; Sanjuán Cortázar, Ana María; Fernández Rodríguez, Manuel A.; Sanz Díez, Roberto

    2012-01-01

    Dihydrobenzo[a]fluorene derivatives have been prepared by a formal intramolecular [3 + 3] cycloaddition of o-alkynylstyrenes bearing a secondary alkyl group at the β-position of the styrene moiety. The process, catalyzed by a cationic gold(I) complex, involves a 1,2-hydride migration as the key step. 6,11-Dihydro-5H-benzo[a]fluorenes could be obtained from the initially generated 6,6a-dihydro-5H-benzo[a]fluorenes by subsequent heating of the reaction mixture under gold(I) or Brønsted acid cat...

  19. Total Synthesis of Sporolide B and 9-epi-Sporolide B

    OpenAIRE

    Nicolaou, K. C.; Wang, Jianhua; Tang, Yefeng; Botta, Lorenzo

    2010-01-01

    The total synthesis of the structurally unique secondary metabolite sporolide B (1b, Figure 1) is described. The total synthesis of 1b was developed on the basis of preliminary studies that revealed the reactivity of an appropriate o-quinone as a diene system toward a number of indene derivatives as dienophiles, first in intermolecular and thence intramolecular settings. Thus, substrates were devised (37, Scheme 5; 75, Scheme 11) that underwent exquisite intramolecular [4+2] cycloaddition rea...

  20. A thermally-induced, tandem [3,3]-sigmatropic rearrangement/[2 + 2] cycloaddition approach to carbocyclic spirooxindoles

    OpenAIRE

    Brummond, Kay M.; Osbourn, Joshua M

    2010-01-01

    The synthesis of C3-carbocyclic spirooxindoles was realized by way of an intramolecular [2 + 2] cycloaddition reaction between a vinylidene indolin-2-one and an alkyne. The cycloaddition reaction occurs selectively with the distal double bond of the allene, is tolerant of a phenyl and trimethylsilyl group on the terminus of the alkyne, and can be used to access bicyclo[4.2.0]octadienes and bicyclo[5.2.0]nonadienes. The allene precursors are not observed, but are likely intermediates of an inf...

  1. 1,3-dipolar cycloaddition of nitrones and nitrile oxides to 5,5-dimethyl-3-methylenepyrrolidine-2-thione

    OpenAIRE

    Fisera, Lubor; Jaroskova, Libuse; Matejkova, Iveta; Heimgartner, Heinz

    1995-01-01

    A simple synthesis of title compound (3) and a number of different cycloadditions are described. C-Aroyl- and C,N-diphenylnitrones react regio- and stereoselectively to the C=C exocyclic double bond of 3, to give only spirocycloadduct (10). On the other hand, C-phenyl-N-methylnitrone gives a mixture of diastereomeric spirocycloadducts (10) and (11). Nitrile oxides undergo 1,3-dipolar cycloaddition both to the exocyclic C=C and C=S double bonds with subsequent cycloreversion and formation of s...

  2. Revealing Stepwise Mechanisms in Dipolar Cycloaddition Reactions: Computational Study of the Reaction between Nitrones and Isocyanates.

    Science.gov (United States)

    Darù, Andrea; Roca-López, David; Tejero, Tomás; Merino, Pedro

    2016-01-15

    The mechanism of cycloaddition reactions of nitrones with isocyanates has been studied using density functional theory (DFT) methods at the M06-2X/cc-pVTZ level of theory. The exploration of the potential energy surfaces associated with two reactive channels leading to 1,2,4-oxadiazolidin-5-ones and 1,4,2-dioxazolidines revealed that the cycloaddition reaction takes place through a concerted mechanism in gas phase and in apolar solvents but a stepwise mechanism in polar solvents. In stepwise mechanisms, the first step of the reaction is a rare case in which the nitrone oxygen acts as a nucleophile by attacking the central carbon atom of the isocyanate (interacting with the π-system of the C═O bond) to give an intermediate. The corresponding transition structure is stabilized by an attractive electrostatic interaction favored in a polar medium. The second step of the reaction is the rate-limiting one in which the formation of 1,2,4-oxadiazolidin-5-ones or 1,4,2-dioxazolidines is decided. Calculations indicate that formation of 1,2,4-oxadiazolidin-5-ones is favored both kinetically and thermodynamically independently of the solvent, in agreement with experimental observations. Noncovalent interactions (NCI) and topological analysis of the gradient field of electron localization function (ELF) bonding confirmed the observed interactions. PMID:26682934

  3. Accelerating Strain-Promoted Azide-Alkyne Cycloaddition Using Micellar Catalysis.

    Science.gov (United States)

    Anderton, Grant I; Bangerter, Alyssa S; Davis, Tyson C; Feng, Zhiyuan; Furtak, Aric J; Larsen, Jared O; Scroggin, Triniti L; Heemstra, Jennifer M

    2015-08-19

    Bioorthogonal conjugation reactions such as strain-promoted azide-alkyne cycloaddition (SPAAC) have become increasingly popular in recent years, as they enable site-specific labeling of complex biomolecules. However, despite a number of improvements to cyclooctyne design, reaction rates for SPAAC remain significantly lower than those of the related copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Here we explore micellar catalysis as a means to increase reaction rate between a cyclooctyne and hydrophobic azide. We find that anionic and cationic surfactants provide the most efficient catalysis, with rate enhancements of up to 179-fold for reaction of benzyl azide with DIBAC cyclooctyne. Additionally, we find that the presence of surfactant can provide up to 51-fold selectivity for reaction with a hydrophobic over hydrophilic azide. A more modest, but still substantial, 11-fold rate enhancement is observed for micellar catalysis of the reaction between benzyl azide and a DIBAC-functionalized DNA sequence, demonstrating that micellar catalysis can be successfully applied to hydrophilic biomolecules. Together, these results demonstrate that micellar catalysis can provide higher conjugation yields in reduced time when using hydrophobic SPAAC reagents. PMID:26056848

  4. On the Mechanism of Copper(I)-Catalyzed Azide-Alkyne Cycloaddition.

    Science.gov (United States)

    Zhu, Lei; Brassard, Christopher J; Zhang, Xiaoguang; Guha, P M; Clark, Ronald J

    2016-06-01

    The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction regiospecifically produces 1,4-disubstituted-1,2,3-triazole molecules. This heterocycle formation chemistry has high tolerance to reaction conditions and substrate structures. Therefore, it has been practiced not only within, but also far beyond the area of heterocyclic chemistry. Herein, the mechanistic understanding of CuAAC is summarized, with a particular emphasis on the significance of copper/azide interactions. Our analysis concludes that the formation of the azide/copper(I) acetylide complex in the early stage of the reaction dictates the reaction rate. The subsequent triazole ring-formation step is fast and consequently possibly kinetically invisible. Therefore, structures of substrates and copper catalysts, as well as other reaction variables that are conducive to the formation of the copper/alkyne/azide ternary complex predisposed for cycloaddition would result in highly efficient CuAAC reactions. Specifically, terminal alkynes with relatively low pKa values and an inclination to engage in π-backbonding with copper(I), azides with ancillary copper-binding ligands (aka chelating azides), and copper catalysts that resist aggregation, balance redox activity with Lewis acidity, and allow for dinuclear cooperative catalysis are favored in CuAAC reactions. Brief discussions on the mechanistic aspects of internal alkyne-involved CuAAC reactions are also included, based on the relatively limited data that are available at this point. PMID:27216993

  5. Light-driven nitrile imine-mediated tetrazole-ene cycloaddition as a versatile platform for fullerene conjugation.

    Science.gov (United States)

    Sugawara, Yuuki; Jasinski, Nils; Kaupp, Michael; Welle, Alexander; Zydziak, Nicolas; Blasco, Eva; Barner-Kowollik, Christopher

    2015-08-21

    An efficient methodology for modular fullerene functionalization via the photo-induced nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) is introduced. The versatility and platform character of the method is illustrated by the light-driven reaction of fullerenes with small molecule, polymeric and surface-immobilized tetrazoles. The efficient fullerene conjugation is evidenced via mass spectrometric techniques. PMID:26179054

  6. Uncovering the Role of Metal Catalysis in Tetrazole Formation by an In Situ Cycloaddition Reaction: An Experimental Approach.

    Science.gov (United States)

    Zhong, Di-Chang; Wen, Ya-Qiong; Deng, Ji-Hua; Luo, Xu-Zhong; Gong, Yun-Nan; Lu, Tong-Bu

    2015-09-28

    Using an experimental approach, the role of metal catalysis has been investigated in the in situ cycloaddition reaction of nitrile with azide to form tetrazoles. It has been shown that metal catalysis serves to activate the cyano group in the nitrile reagent by a coordinative interaction. PMID:26293313

  7. Microwave-Enhanced Organic Syntheses for the Undergraduate Laboratory: Diels-Alder Cycloaddition, Wittig Reaction, and Williamson Ether Synthesis

    Science.gov (United States)

    Baar, Marsha R.; Falcone, Danielle; Gordon, Christopher

    2010-01-01

    Microwave heating enhanced the rate of three reactions typically performed in our undergraduate organic chemistry laboratory: a Diels-Alder cycloaddition, a Wittig salt formation, and a Williamson ether synthesis. Ninety-minute refluxes were shortened to 10 min using a laboratory-grade microwave oven. In addition, yields improved for the Wittig…

  8. Construction of the Core of Pseudolaric Acid A and Mechanistic Studies on Intramolecular [4+3] Cycloaddition

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    This paper describes the construction of hemiacetal 2, the core of pseudolaric acid A via oxidative cleavage of acetonide 6 or 7 and enolization-hemiacetalization of aldehyde 8. A plausible general mechanism for the intramolecular [4+3] cycloaddition of sulfoxide 4 to adduct 3 is suggested.

  9. Synthesis of some novel fluoro isoxazolidine and isoxazoline derivatives using -benzyl fluoro nitrone via cycloaddition reaction in ionic liquid

    Indian Academy of Sciences (India)

    Bhaskar Chakraborty; Govinda Prasad Luitel

    2013-09-01

    1-Butyl-3-methylimidazolium-based ionic liquids are found to accelerate significantly the intermolecular 1,3-dipolar cycloaddition of -benzyl-fluoro nitrone derived in situ from 2,6-difluoro benzaldehyde and -benzylhydroxylamine, with activated alkenes and electron deficient alkynes to afford enhanced rates and improved yields of novel isoxazolidines and isoxazolines.

  10. Asymmetric azidation-cycloaddition with open-chain peptide-based catalysts. A sequential enantioselective route to triazoles.

    Science.gov (United States)

    Guerin, David J; Miller, Scott J

    2002-03-13

    A family of beta-substituted histidine-containing peptides has been synthesized to probe the effect of noncovalent conformational rigidification on catalyst enantioselectivity. Unambiguous enhancement of enantioselectivity in the conjugate addition of azide to alpha,beta-unsaturated carboxylate derivatives has been achieved, enabling application to a sequential asymmetric azidation/cycloaddition for the synthesis of optically enriched triazoles and triazolines. PMID:11878965

  11. AOT-based microemulsions accelerate the 1,3-cycloaddition of benzonitrile oxide to N-ethylmaleimide

    NARCIS (Netherlands)

    Engberts, J. B. F. N.; Fernandez, E.; Garcia-Rio, L.; Leis, J. R.

    2006-01-01

    We studied the 1,3-dipolar cycloaddition of benzonitrile oxide to N-ethylmaleimide in AOT/isooctane/water microemulsions at 25.0 degrees C and found the reaction rate to be roughly 150 and 35 times greater than that in isooctane and pure water, respectively. The accelerating effect of the microemuls

  12. Theoretical Study on the Mechanism of the Cycloaddition Reaction between Stannylene and Ethylene or Formaldehyde

    Institute of Scientific and Technical Information of China (English)

    卢秀慧; 翟利民; 王沂轩

    2001-01-01

    The mechanism of the cycloaddition reaction of singlet stannylene and ethylene or formaldehyde has been studied by using density functional theory, The geometrical parameters, h-armonic vibrational frequencies and energies of stationary points for potential energy surface are calculated by RB3LYP/3-21G* method. The results show that the two reaction proceesses are both two steps: (1) stannylene and ethylene or formaldehyde form an energy-rich intermediate complex respectively, which is an exothermal reaction with no barrier;(2) two intermediate complexes isomerize to the product, respectively, with the barriers of these two reactions being 52.97and 45.15 kJ/mol at RB3LYP/3-21G* level.

  13. Bottlenecks in the prediction of regioselectivity of [4 + 2] cycloaddition reactions: An assessment of reactivity descriptors

    Indian Academy of Sciences (India)

    G Gayatri; G Narahari Sastry

    2005-09-01

    B3LYP/6-31G() calculations were performed to obtain all the transition states and products for the 128 distinct reaction channels of Diels-Alder reactions by taking all possible combinations from a series of dienes (1N-a, 1N-b, 2N, 1P-a, 1P-b, 2P, 1O, 1S) and dienophiles (NE, PE, OE, SE, AE, OHE, MeE, CNE). The predictive ability of the values to gauge the regioselectivity of the putative [4 + 2] cycloaddition reactions is analysed. No correlation is obtained between the reaction energies and activation energies. The extent of asynchronicity is measured based on the bond order analysis. DFT-based descriptors such as the local softness ($s^{+}_{k}$ and $s_{k}^{-}$), Fukui function indices ($f^{+}_{k}$ and $f_{k}^{-}$), global electrophilicity index () and local electrophilicity index () were found to be better than the conventional FMO predictions.

  14. Theoretical Study on the Mechanism of the Cycloaddition Reaction between Alkylidene Carbene and Ethylene

    Institute of Scientific and Technical Information of China (English)

    LU,Xiu-Hui(卢秀慧); ZHAI,Li-Min(翟利民); WU,Wei-Rong(武卫荣)

    2004-01-01

    The mechanism of cycloaddition reaction between singlet alkylidene carbene and ethylene has been investigated with second-order Moller-Plesset perturbation theory (MP2). By using 6-31G* basis , geometry optimization, vibrational analysis and energetics have been calculated for the involved stationary points on the potential energy surface. The results show that the title reaction has two major competition channels. An energy-rich intermediate (INT) is firstly formed between alkylidene carbene and ethylene through a barrier-free exothermic reaction of 63.62 kJ/mol, and the intermediate then isomerizes to a three-membered ring product (P1) and a four-memberd ring product (P2) via transition state TS1 and TS2, in which energy barriers are 47.00 and 51.02 kJ/mol, respectively. P1 is the main product.

  15. Electronic effects of ruthenium-catalyzed [3+2]-cycloaddition of alkynes and azides

    KAUST Repository

    Hou, Duenren

    2010-11-01

    A combined experimental and theoretical study of ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) reactions is presented and various electronic analyses were conducted to provide a basis in understanding the observed regioselectivity of the 1,2,3-triazole products. Computational studies using density functional theory (DFT) and atoms in molecules quantum theory (AIM) further yield fresh details on the electronic factors that determine the regioselectivity in the RuAAC. It is found that the formation of 1,2,3-triazole products is irreversible and from the Hammett study, the pathway involving a vinyl cationic intermediate is ruled out. The electronic effect favors the formation of 5-electron-donating-group substituted-1,2,3-trizoles. © 2010 Elsevier Ltd. All rights reserved.

  16. Azide-Alkyne Huisgen [3+2] Cycloaddition Using CuO Nanoparticles

    Directory of Open Access Journals (Sweden)

    Hyunjoon Song

    2012-11-01

    Full Text Available Recent developments in the synthesis of CuO nanoparticles (NPs and their application to the [3+2] cycloaddition of azides with terminal alkynes are reviewed. With respect to the importance of click chemistry, CuO hollow NPs, CuO hollow NPs on acetylene black, water-soluble double-hydrophilic block copolymer (DHBC nanoreactors and ZnO–CuO hybrid NPs were synthesized. Non-conventional energy sources such as microwaves and ultrasound were also applied to these click reactions, and good catalytic activity with high regioselectivity was observed. CuO hollow NPs on acetylene black can be recycled nine times without any loss of activity, and water-soluble DHBC nanoreactors have been developed for an environmentally friendly process.

  17. Cycloaddition mechanism for the resin-OsO4-catalyzed of styrene: A DFT study

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The postulated intermediates in the base-free and base-assisted addition of OsO4 to styrene have been investigated at the B3LYP/6-311G** level of the theory. N(CH3)2(Ph) was chosen as the base of the resin-OsO4. According to our model calculations the [2+3] addition was found to be favorable with an activation of <45.00 kJ/mol. In contract, the reaction barriers for the [2+2] cycloaddition remain high (>155.00 kJ/mol). In addition, the electronic structure analysis of the molecules was carried out by na- ture bond orbital (NBO). The computational results were in reasonable agreement with experimental results.

  18. Cycloaddition mechanism for the resin-OsO4-catalyzed of styrene: A DFT study

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The postulated intermediates in the base-free and base-assisted addition of OsO4 to styrene have been investigated at the B3LYP/6-311G** level of the theory. N(CH3)2(Ph) was chosen as the base of the resin-OsO4. According to our model calculations the [2+3] addition was found to be favorable with an activation of <45.00 Kj/mol. In contract, the reaction barriers for the [2+2] cycloaddition remain high (>155.00 Kj/mol). In addition, the electronic structure analysis of the molecules was carried out by nature bond orbital (NBO). The computational results were in reasonable agreement with experimental results.

  19. A combined experimental and theoretical study of the thermal cycloaddition of aryl azides with activated alkenes.

    Science.gov (United States)

    Zeghada, Sarah; Bentabed-Ababsa, Ghenia; Derdour, Aïcha; Abdelmounim, Safer; Domingo, Luis R; Sáez, José A; Roisnel, Thierry; Nassar, Ekhlass; Mongin, Florence

    2011-06-01

    Reactions were performed from aryl azides on the one hand, and activated alkenes coming from β-dicarbonyl compounds or malonodinitrile on the other hand, either with recourse to conventional heating or to microwave activation, to afford 1-aryl-1H-1,2,3-triazoles. The mechanism and the regioselectivity of the reactions involving β-dicarbonyl compounds have been theoretically studied using DFT methods at the B3LYP/6-31G* level: they are domino processes comprising a tautomeric equilibrium of the β-dicarbonyl compounds with their enol forms, a 1,3-dipolar cycloaddition of the enol forms with the aryl azides (high activation energy), and a dehydration process (lower activation energy). The effect of non-conventional activation methods on the degradation of 1,2,3-triazolines was next studied experimentally. Finally, some of the 1,2,3-triazoles such synthesized were evaluated for their bactericidal and cytotoxic activities. PMID:21494704

  20. Enhancing the reactivity of 1,2-diphospholes in cycloaddition reactions.

    Science.gov (United States)

    Zagidullin, Almaz; Miluykov, Vasili; Oshchepkova, Elena; Tufatullin, Artem; Kataeva, Olga; Sinyashin, Oleg

    2015-01-01

    Two different approaches have been employed to enhance the reactivity of 1-alkyl-1,2-diphospholes - the introduction of electron-withdrawing groups either at the phosphorus atoms or in the para-position of the arene ring. The alkylation of sodium 1,2-diphospha-3,4,5-triphenylcyclopentadienide with alkyl halides Hal-CH2-R (R = CN, COOEt, OMe, CH2OEt) results in corresponding 1-alkyl-3,4,5-triphenyl-1,2-diphospholes (alkyl = CH2CN (1a), CH2COOEt (1b), CH2OMe (1c), and (CH2)2OEt (1d)), which spontaneously undergo the intermolecular [4 + 2] cycloaddition reactions at room temperature to form the mixture of the cycloadducts, 2a-c, respectively. However the alkylation of sodium 1,2-diphospha-3,4,5-tri(p-fluorophenyl)cyclopentadienide with ethyl iodide leads to stable 1-ethyl-3,4,5-tris(p-fluorophenyl)-1,2-diphosphole (1e), which forms the [4 + 2] cycloadduct 2,3,4,4a,5,6-hexa(p-fluorophenyl)-1-ethyl-1,7,7a-triphospha-4,7-(ethylphosphinidene)indene (2e) only upon heating up to 60 °C. With further heating to 120 °C with N-phenylmaleimide, the cycloadducts 2a-c and 2e undergo the retro-Diels-Alder reaction and form only one product of the [4 + 2] cycloaddition reaction 3a-с, 3e with good yields up to 65%. PMID:25815066

  1. Efficient synthesis of functionalized 1,2,3-triazoles by catalyst-free 1,3-dipolar cycloaddition of nitroalkenes with sodium azide

    International Nuclear Information System (INIS)

    A simple and efficient protocol has been developed for the synthesis of 1,2,3-triazole derivatives by catalyst-free 1,3-dipolar cycloaddition of nitroalkenes with sodium azide under mild conditions (author)

  2. Total protein

    Science.gov (United States)

    The total protein test measures the total amount of two classes of proteins found in the fluid portion of your ... nutritional problems, kidney disease or liver disease . If total protein is abnormal, you will need to have more ...

  3. Total protein

    Science.gov (United States)

    ... page: //medlineplus.gov/ency/article/003483.htm Total protein To use the sharing features on this page, please enable JavaScript. The total protein test measures the total amount of two classes ...

  4. Catalytic Asymmetric Total Synthesis of Hedyosumins A, B, and C.

    Science.gov (United States)

    Sun, Wang-Bin; Wang, Xuan; Sun, Bing-Feng; Zou, Jian-Ping; Lin, Guo-Qiang

    2016-03-18

    The first and asymmetric total synthesis of hedyosumins A, B, and C was accomplished in 13-14 steps from simple starting materials. The essential tools that allow us to access the tetracyclic skeleton include an organocatalytic [4 + 3] cycloaddition reaction, an intramolecular aldol condensation, and an intramolecular carboxymercuration/demercuration enabled lactonization. A CBS-catalyzed asymmetric reduction was employed to boost the ee of the synthetic natural products to an excellent level. This synthesis established the absolute configurations of hedyosumins A, B, and C. PMID:26925758

  5. Formal [4+2] cycloaddition of di-tert-butyl 2-ethoxycyclobutane-1,1-dicarboxylate with ketones or aldehydes and tandem lactonization.

    Science.gov (United States)

    Okado, Ryohei; Nowaki, Aya; Matsuo, Jun-Ichi; Ishibashi, Hiroyuki

    2012-01-01

    A catalytic amount of tin(IV) chloride catalyzed formal [4+2] cycloaddition reaction of di-tert-butyl 2-ethoxycyclobutane-1,1-carboxylate with ketones or aldehydes to give diethyl 6-ethoxydihydro-2H-pyran-3,3(4H)-dicarboxylates, whereas two equivalents of trimethylsilyl triflate promoted tandem [4+2] cycloaddition and lactonization to afford 3-oxo-2,6-dioxabicyclo[2.2.2]octane-4-carboxylate esters. PMID:22223370

  6. Formal [4+2] Cycloaddition of di-tert-Butyl 2-Ethoxycyclobutane-1,1-dicarboxylate with Ketones or Aldehydes and Tandem Lactonization

    OpenAIRE

    Okado, Ryohei; Nowaki, Aya; Matsuo, Jun-ichi; Ishibashi, Hiroyuki

    2012-01-01

    A catalytic amount of tin(IV) chloride catalyzed formal [4+2] cycloaddition reaction of di-tert-butyl 2-ethoxycyclobutane-1,1-carboxylate with ketones or aldehydes to give diethyl 6-ethoxydihydro-2H-pyran-3,3(4H)-dicarboxylates, whereas two equivalents of trimethylsilyl triflate promoted tandem [4+2] cycloaddition and lactonization to afford 3-oxo-2,6-dioxabicyclo[2.2.2]octane-4-carboxylate esters.

  7. Nickel-Catalyzed Intramolecular [3 + 2 + 2] Cycloadditions of Alkylidenecyclopropanes. A Straightforward Entry to Fused 6,7,5-Tricyclic Systems

    OpenAIRE

    Saya Codesal, Lucía; Fernández, Israel; López, Fernando; Mascareñas Cid, José Luis

    2014-01-01

    A highly diastereo- and chemoselective intramolecular nickel-catalyzed cycloaddition of alkene- and alkyne-tethered alkynylidenecyclopropanes is reported. The method constitutes the first fully intramolecular [3 + 2 + 2] alkylidenecyclopropropane cycloaddition occurring via a proximal cleavage of the cyclopropane and makes it possible to build relevant 6,7,5-tricyclic frameworks in a single-pot reaction. Importantly, the reaction outcome is highly dependent on the characteristics of the nicke...

  8. Improving the tensile strength of carbon nanotube yarn via one-step double [2+1] cycloadditions

    Energy Technology Data Exchange (ETDEWEB)

    Kim, HeeJin [Kyungpook National University, Daegu (Korea, Republic of); Lee, Jaegeun; Park, Byungrak; Sa, Jeong Hoon; Jung, Alum; Kim, Teawon; Park, Junbeom; Hwang, Woonbong; Lee, Kun Hong [Pohang University of Science and Technology, Pohang (Korea, Republic of)

    2016-01-15

    The tensile strength of a CNT yarn was improved through simple one-step double [2+1] cycloaddition reactions that crosslinked the constituent CNTs using a polyethylene glycol (PEG)-diazide crosslinker. The FT-IR spectrum confirmed that the azide groups in the PEG-diazide were converted into aziridine rings, indicating that the cycloaddition reaction was successful. The generation of crosslinked CNTs was also supported by the observation of N1s peak in the XPS spectrum and the increased thermal stability of the material, as observed by TGA. The tensile strength of the CNT yarn was increased from 0.2GPa to 1.4GPa after the crosslinking reaction when twisted at 4000 twists/ meter. The appropriate selection of the crosslinker may further optimize the CNT yarn crosslinking reaction. The simplicity of this one-step crosslinking reaction provides an economical approach to the mass production of high-strength CNT yarns.

  9. Nucleophile-directed selectivity towards linear carbonates in the niobium pentaethoxide-catalysed cycloaddition of CO2 and propylene oxide

    KAUST Repository

    Dutta, Barnali

    2014-01-01

    Homoleptic Nb-complexes combined with selected organic nucleophiles generate very active catalytic systems for the cycloaddition of propylene oxide and CO2 under ambient conditions. An unprecedented reaction pathway towards an acyclic organic carbonate is observed when extending the study to [Nb(OEt)5] in combination with 4-dimethylamino-pyridine (DMAP) or tetra-n-butylammonium bromide (TBAB). Mechanistic insights of the reaction are provided based on experimental and spectroscopic evidences. This journal is © the Partner Organisations 2014.

  10. Growth of Fullerene Fragments Using the Diels-Alder Cycloaddition Reaction: First Step towards a C60 Synthesis by Dimerization

    Directory of Open Access Journals (Sweden)

    Julio A. Alonso

    2013-02-01

    Full Text Available Density Functional Theory has been used to model the Diels-Alder reactions of the fullerene fragments triindenetriphenilene and pentacyclopentacorannulene with ethylene and 1,3-butadiene. The purpose is to prove the feasibility of using Diels-Alder cycloaddition reactions to grow fullerene fragments step by step, and to dimerize fullerene fragments, as a way to obtain C60. The dienophile character of the fullerene fragments is dominant, and the reaction of butadiene with pentacyclopentacorannulene is favored.

  11. Synthesis of 2-azaspiro[4.4]nonan-1-ones via phosphine-catalysed [3+2]-cycloadditions

    Energy Technology Data Exchange (ETDEWEB)

    Yong, Sarah R.; Williams, Morwenna C.; Pyne, Stephen G.; Ung, Alison T.; Skelton, Brian W.; White, Allan H.; Turner, Peter (UWA); (Wollongong); (Sydney)

    2008-10-03

    The phosphine-catalyzed [3+2]-cycloaddition of the 2-methylene {gamma}-lactams 4 and 5 and the acrylate 6 with the ylides derived from the ethyl ester, the amide or the chiral camphor sultam derivative of 2-butynoic acid (7a-c) give directly, or indirectly after reductive cyclization, spiro-heterocyclic products. The acid 32 underwent Curtius rearrangement and then acid hydrolysis to give two novel spiro-cyclic ketones, 41 and 42.

  12. Multicomponent Dipolar Cycloaddition Strategy: Combinatorial Synthesis of Novel Spiro-Tethered Pyrazolo[3,4-b]quinoline Hybrid Heterocycles.

    Science.gov (United States)

    Sumesh, Remani Vasudevan; Muthu, Muthumani; Almansour, Abdulrahman I; Suresh Kumar, Raju; Arumugam, Natarajan; Athimoolam, S; Jeya Yasmi Prabha, E Arockia; Kumar, Raju Ranjith

    2016-05-01

    The stereoselective syntheses of a library of novel spiro-tethered pyrazolo[3,4-b]quinoline-pyrrolidine/pyrrolothiazole/indolizine-oxindole/acenaphthene hybrid heterocycles have been achieved through the 1,3-dipolar cycloaddition of azomethine ylides generated in situ from α-amino acids and 1,2-diketones to dipolarophiles derived from pyrazolo[3,4-b]quinoline derivatives. PMID:27027478

  13. Enzyme-catalysed [4+2] cycloaddition is a key step in the biosynthesis of spinosyn A.

    Science.gov (United States)

    Kim, Hak Joong; Ruszczycky, Mark W; Choi, Sei-hyun; Liu, Yung-nan; Liu, Hung-wen

    2011-05-01

    The Diels-Alder reaction is a [4+2] cycloaddition reaction in which a cyclohexene ring is formed between a 1,3-diene and an electron-deficient alkene via a single pericyclic transition state. This reaction has been proposed as a key transformation in the biosynthesis of many cyclohexene-containing secondary metabolites. However, only four purified enzymes have thus far been implicated in biotransformations that are consistent with a Diels-Alder reaction, namely solanapyrone synthase, LovB, macrophomate synthase, and riboflavin synthase. Although the stereochemical outcomes of these reactions indicate that the product formation could be enzyme-guided in each case, these enzymes typically demonstrate more than one catalytic activity, leaving their specific influence on the cycloaddition step uncertain. In our studies of the biosynthesis of spinosyn A, a tetracyclic polyketide-derived insecticide from Saccharopolyspora spinosa, we identified a cyclase, SpnF, that catalyses a transannular [4+2] cycloaddition to form the cyclohexene ring in spinosyn A. Kinetic analysis demonstrates that SpnF specifically accelerates the ring formation reaction with an estimated 500-fold rate enhancement. A second enzyme, SpnL, was also identified as responsible for the final cross-bridging step that completes the tetracyclic core of spinosyn A in a manner consistent with a Rauhut-Currier reaction. This work is significant because SpnF represents the first example characterized in vitro of a stand-alone enzyme solely committed to the catalysis of a [4+2] cycloaddition reaction. In addition, the mode of formation of the complex perhydro-as-indacene moiety in spinosyn A is now fully established. PMID:21544146

  14. Quarternization of 3-azido-1-propyne oligomers obtained by copper(I)-catalyzed azide–alkyne cycloaddition polymerization

    OpenAIRE

    Shun Nakano; Akihito Hashidzume; Takahiro Sato

    2015-01-01

    3-Azido-1-propyne oligomer (oligoAP) samples, prepared by copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) polymerization, were quarternized quantitatively with methyl iodide in sulfolane at 60 °C to obtain soluble oligomers. The conformation of the quarternized oligoAP in dilute DMSO-d6 solution was examined by pulse-field-gradient spin-echo NMR based on the touched bead model.

  15. An Efficient Synthesis of Novel Dispirooxindole Derivatives via One-Pot Three-Component 1,3-Dipolar Cycloaddition Reactions

    OpenAIRE

    Yucheng Wang; Juxian Wang; Hongtao Liu; Huiyuan Wang; Wei Lin; Lexing Xu; Zhibin Huang; Gang Chen; Qian Zhao; Daqing Shi

    2012-01-01

    A series of novel dispirooxindoles have been synthesized through three-component 1,3-dipolar cycloaddition of azomethine ylides generated in situ by the decarboxylative condensation of isatin and an α-amino acid with the dipolarophile 5-benzylidene-1,3-dimethylpyrimidine-2,4,6-trione. This method has the advantages of mild reaction conditions, high atom economy, excellent yields, and high regio- and stereo-selectivity.

  16. The fascinating construction of pyridine ring systems by transition metal-catalysed [2 + 2 + 2] cycloaddition reactions.

    Science.gov (United States)

    Heller, Barbara; Hapke, Marko

    2007-07-01

    Cycloaddition reactions compose one of the most important classes of reactions when it comes to the simultaneous formation of several bonds in one reaction step. The de novo construction of carbocyclic aromatic systems from acetylenes was also found as an excellent possibility for the assembly of heteroaromatic systems. The transition metal-catalysed [2 + 2 + 2] cycloaddition reaction constitutes a fascinating tool for the synthesis of pyridines from nitriles and the most recent developments demonstrate the ability to control the substitution pattern as well as the possibility of introducing chirality by the use of achiral substrates and a chiral catalyst under mild conditions. In this tutorial review we are focusing on the de novo construction of pyridine ring systems by the transition metal-catalysed [2 + 2 + 2] cycloaddition reaction. After surveying the mechanistic features and intermediates of the reaction depending on the different metal complexes used, we depict the preparation of achiral pyridine derivatives. The last section describes the advances in the synthesis of chiral pyridines and biaryls using the cyclotrimerization method. The various possibilities of introducing chirality by catalytic means are presented and illustrated by instructive examples. This review will be of interest for people active in: Organic Chemistry, Organometallic Chemistry, Transition Metal Chemistry, Stereoselective Synthesis, Heterocyclic Chemistry. PMID:17576476

  17. Total algorithms

    NARCIS (Netherlands)

    Tel, G.

    1993-01-01

    We define the notion of total algorithms for networks of processes. A total algorithm enforces that a "decision" is taken by a subset of the processes, and that participation of all processes is required to reach this decision. Total algorithms are an important building block in the design of distri

  18. Metal ion-catalyzed cycloaddition vs hydride transfer reactions of NADH analogues with p-benzoquinones.

    Science.gov (United States)

    Fukuzumi, S; Fujii, Y; Suenobu, T

    2001-10-24

    1-Benzyl-4-tert-butyl-1,4-dihydronicotinamide (t-BuBNAH) reacts efficiently with p-benzoquinone (Q) to yield a [2+3] cycloadduct (1) in the presence of Sc(OTf)(3) (OTf = OSO(2)CF(3)) in deaerated acetonitrile (MeCN) at room temperature, while no reaction occurs in the absence of Sc(3+). The crystal structure of 1 has been determined by the X-ray crystal analysis. When t-BuBNAH is replaced by 1-benzyl-1,4-dihydronicotinamide (BNAH), the Sc(3+)-catalyzed cycloaddition reaction of BNAH with Q also occurs to yield the [2+3] cycloadduct. Sc(3+) forms 1:4 complexes with t-BuBNAH and BNAH in MeCN, whereas there is no interaction between Sc(3+) and Q. The observed second-order rate constant (k(obs)) shows a first-order dependence on [Sc(3+)] at low concentrations and a second-order dependence at higher concentrations. The first-order and the second-order dependence of the rate constant (k(et)) on [Sc(3+)] was also observed for the Sc(3+)-promoted electron transfer from CoTPP (TPP = tetraphenylporphyrin dianion) to Q. Such dependence of k(et) on [Sc(3+)] is ascribed to formation of 1:1 and 1:2 complexes between Q(*)(-) and Sc(3+) at the low and high concentrations of Sc(3+), respectively, which results in acceleration of the rate of electron transfer. The formation constants for the 1:2 complex (K(2)) between the radical anions of a series of p-benzoquinone derivatives (X-Q(*)(-)) and Sc(3+) are determined from the dependence of k(et) on [Sc(3+)]. The K(2) values agree well with those determined from the dependence of k(obs) on [Sc(3+)] for the Sc(3+)-catalyzed addition reaction of t-BuBNAH and BNAH with X-Q. Such an agreement together with the absence of the deuterium kinetic isotope effects indicates that the addition proceeds via the Sc(3+)-promoted electron transfer from t-BuBNAH and BNAH to Q. When Sc(OTf)(3) is replaced by weaker Lewis acids such as Lu(OTf)(3), Y(OTf)(3), and Mg(ClO(4))(2), the hydride transfer reaction from BNAH to Q also occurs besides the

  19. Antifouling coatings based on covalently cross-linked agarose film via thermal azide-alkyne cycloaddition.

    Science.gov (United States)

    Xu, Li Qun; Pranantyo, Dicky; Neoh, Koon-Gee; Kang, En-Tang; Teo, Serena Lay-Ming; Fu, Guo Dong

    2016-05-01

    Coatings based on thin films of agarose-poly(ethylene glycol) (Agr-PEG) cross-linked systems are developed as environmentally-friendly and fouling-resistant marine coatings. The Agr-PEG cross-linked systems were prepared via thermal azide-alkyne cycloaddition (AAC) using azido-functionalized Agr (AgrAz) and activated alkynyl-containing poly(2-propiolamidoethyl methacrylate-co-poly(ethylene glycol)methyl ether methacrylate) P(PEMA-co-PEGMEMA) random copolymers as the precursors. The Agr-PEG cross-linked systems were further deposited onto a SS surface, pre-functionalized with an alkynyl-containing biomimetic anchor, dopamine propiolamide, to form a thin film after thermal treatment. The thin film-coated SS surfaces can effectively reduce the adhesion of marine algae and the settlement of barnacle cyprids. Upon covalent cross-linking, the covalently cross-linked Agr-PEG films coated SS surfaces exhibit good stability in flowing artificial seawater, and enhanced resistance to the settlement of barnacle cyprids, in comparison to that of the surfaces coated with physically cross-linked AgrAz films. PMID:26836479

  20. C-(4-[18F]fluorophenyl)-N-phenyl nitrone: A novel 18F-labeled building block for metal free [3+2]cycloaddition

    International Nuclear Information System (INIS)

    Radiofluorination via [3+2]-nitrone-alkene cycloaddition was studied using the model reaction between 18F-labeled C-(4-fluorophenyl)-N-phenyl nitrone ([18F]1) and substituted maleimides 2a–c. [18F]1 was prepared in RCY of 73.6±5.8% and radiochemical purity of >95%. Cycloaddition of [18F]1 to 2a in toluene at 80 °C and in EtOH at 110 °C gave the respective isoxazolidine [18F]5a in >80% RCY at 10 min reaction time. Reaction between [18F]1 and 2b, c also went smoothly to afford the respective cycloaddition products in high radiochemical yields. - Highlights: ► [2+3]-Nitrone-alkene metal-free cycloaddition for radiolabelling. ► Optimized radiosynthesis of C-(4-[18F]fluorophenyl)-N-phenyl nitrone ([18F]1). ► Fast and high-yielding cycloaddition of [18F]1 to model maleimides.

  1. Experimental and theoretical approaches to [1,5]-prototropic generation of an azomethine ylide and a 1,3-dipolar cycloaddition for novel spiropyrrolidine oxindoles synthesis

    Science.gov (United States)

    Sarrafi, Yaghoub; Hamzehloueian, Mahshid; Alimohammadi, Kamal; Yeganegi, Saeid

    2012-12-01

    A series of spiropyrrolidine oxindoles was synthesized via a multicomponent 1,3-dipolar cycloaddition reaction of isatin, benzylamine and chalcone derivatives. The regio- and stereochemistry of the products were established by single crystal X-ray structure and spectroscopic techniques. The molecular mechanism of this cycloaddition has been investigated by means of a density functional theory (DFT) method. The energy path in preparing the azomethine ylide via a [1,5]-H shift in an iminium ion was evaluated. The regio- and stereoselectivity were explained on the basis of transition states stabilities, global and local reactivity indices of the reactants. The cycloaddition has been assumed to take place through one-step pathway in which two C-C bonds are formed in a nonsynchronous way.

  2. A DFT study on the mechanisms for the cycloaddition reactions between 1-aza-2-azoniaallene cations and acetylenes.

    Science.gov (United States)

    Wang, Jing-mei; Li, Zhi-ming; Wang, Quan-rui; Tao, Feng-gang

    2013-01-01

    The mechanisms of cycloaddition reactions between 1-aza-2-azoniaallene cations 1 and acetylenes 2 have been investigated using the global electrophilicity and nucleophilicity of the corresponding reactants as global reactivity indexes defined within the conceptual density functional theory. The reactivity and regioselectivity of these reactions were predicted by analysis of the energies, geometries, and electronic nature of the transition state structures. The theoretical results revealed that the reaction features a tandem process: an ionic 1,3-dipolar cycloaddition to produce the cycloadducts 3 H-pyrazolium salts 3 followed by a [1,2]-shift affording the thermodynamically more stable adducts 4 or 5. The mechanism of the cycloaddition reactions can be described as an asynchronous concerted pathway with reverse electron demand. The model reaction has also been investigated at the QCISD/6-31++G(d,p) and CCSD(T)/6-31++G(d,p)//B3LYP/6-31++G(d,p) levels as well as by the DFT. The polarizable continuum model, at the B3LYP/6-31++G(d,p) level of theory, was used to study solvent effects on all the studied reactions. In solvent dichloromethane, all the initial cycloadducts 3 were obtained via direct ionic process as the result of the solvent effect. The consecutive [1,2]-shift reaction, in which intermediates 3 are rearranged to the five-membered heterocycles 4/5, is proved to be a kinetically controlled reaction, and the regioselectivity can be modulated by varying the migrant. The LOL function and RDG function based on localized electron analysis were used to analysis the covalent bond and noncovalent interactions in order to unravel the mechanism of the title reactions. PMID:22810049

  3. Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

    Directory of Open Access Journals (Sweden)

    Regina Berg

    2013-12-01

    Full Text Available The copper-catalyzed azide–alkyne cycloaddition (CuAAC is one of the most broadly applicable and easy-to-handle reactions in the arsenal of organic chemistry. However, the mechanistic understanding of this reaction has lagged behind the plethora of its applications for a long time. As reagent mixtures of copper salts and additives are commonly used in CuAAC reactions, the structure of the catalytically active species itself has remained subject to speculation, which can be attributed to the multifaceted aggregation chemistry of copper(I alkyne and acetylide complexes. Following an introductory section on common catalyst systems in CuAAC reactions, this review will highlight experimental and computational studies from early proposals to very recent and more sophisticated investigations, which deliver more detailed insights into the CuAAC’s catalytic cycle and the species involved. As diverging mechanistic views are presented in articles, books and online resources, we intend to present the research efforts in this field during the past decade and finally give an up-to-date picture of the currently accepted dinuclear mechanism of CuAAC. Additionally, we hope to inspire research efforts on the development of molecularly defined copper(I catalysts with defined structural characteristics, whose main advantage in contrast to the regularly used precatalyst reagent mixtures is twofold: on the one hand, the characteristics of molecularly defined, well soluble catalysts can be tuned according to the particular requirements of the experiment; on the other hand, the understanding of the CuAAC reaction mechanism can be further advanced by kinetic studies and the isolation and characterization of key intermediates.

  4. CO2 Conversion: The Potential of Porous–Organic Polymers (POPs) for the cycloaddition of CO2 and epoxides

    KAUST Repository

    Eddaoudi, Mohamed

    2016-03-30

    Novel porous organic polymers (POPs) have been synthesized using functionalized Cr and Co-salen complexes as molecular building blocks. The integration of metalosalen catalysts into the porous polymers backbone permits the successful utilization of the materials as solid-state catalysts for CO2-epoxide cycloadditions reactions with excellent catalytic performance under mild conditions of temperature and pressure. The catalyst proved to be fully recyclable and robust thus showing the potential of POPs as smart functional materials for the heterogenization of key catalytic elements.

  5. Sequential One-Pot Ruthenium-Catalyzed Azide−Alkyne Cycloaddition from Primary Alkyl Halides and Sodium Azide

    KAUST Repository

    Johansson, Johan R.

    2011-04-01

    An experimentally simple sequential one-pot RuAAC reaction, affording 1,5-disubstituted 1H-1,2,3-triazoles in good to excellent yields starting from an alkyl halide, sodium azide, and an alkyne, is reported. The organic azide is formed in situ by treating the primary alkyl halide with sodium azide in DMA under microwave heating. Subsequent addition of [RuClCp*(PPh 3) 2] and the alkyne yielded the desired cycloaddition product after further microwave irradiation. © 2011 American Chemical Society.

  6. Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

    Energy Technology Data Exchange (ETDEWEB)

    Pham, Tien Q.; Pyne, Stephen G.; Skelton, Brian W.; White, Allan H. (UWA); (Wollongong)

    2010-07-20

    The phosphine-catalyzed [3 + 2]-cycloaddition of 5-methylenehydantoins 4 with the ylides 5, derived from addition of tributylphosphine to the 2-butynoic acid derivatives, 6a-d, gives spiro-heterocyclic products. The camphor sultam derivative 6b gives optically active products. Noteable was that the ylides derived from ethyl 2-butynoate and the 3-(2-butynoyl)-1,3-oxazolidin-2-one derivatives 6c and 6d gave spiro-heterocyclic products with reverse regioselectivities. The N,N-dibenzylprotected cycloadduct has been converted to carbocyclic hydantocidin and 6,7-diepi-carbocyclic hydantocidin.

  7. Synthesis with Perfect Atom Economy: Generation of Furan Derivatives by 1,3-Dipolar Cycloaddition of Acetylenedicarboxylates at Cyclooctynes

    OpenAIRE

    Klaus Banert; Sandra Bochmann; Andreas Ihle; Oliver Plefka; Florian Taubert; Tina Walther; Marcus Korb; Tobias Rüffer; Heinrich Lang

    2014-01-01

    Cyclooctyne and cycloocten-5-yne undergo, at room temperature, a 1,3-dipolar cycloaddition with dialkyl acetylenedicarboxylates 1a,b to generate furan-derived short-lived intermediates 2, which can be trapped by two additional equivalents of 1a,b or alternatively by methanol, phenol, water or aldehydes to yield polycyclic products 3b–d, orthoesters 4a–c, ketones 5 or epoxides 6a,b, respectively. Treatment of bis(trimethylsilyl) acetylenedicarboxylate (1c) with cyclooctyne leads to the ketone ...

  8. An ab initio study of the mechanism of the cycloaddition reaction forming bicyclic compounds between vinylidene (H2C=C:) and ethylene

    OpenAIRE

    YONGQING LI; ZHENXIA LIAN; XIUHUI LU

    2011-01-01

    The mechanism of the cycloaddition reaction forming a bicyclic compounds between singlet vinylidene (H2C=C:) and ethylene was investigated using the CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that this reaction has one dominant channel. The presented rule of this reaction, a [2+2] cycloaddition reaction between the two reactants occurred forming a four-membered ring carbene (INT1), in which the sp lone electron of the C atom from carbene in INT1 and the...

  9. Application of Azide-Alkyne Cycloaddition “Click Chemistry” for the Synthesis of Grb2 SH2 Domain-Binding Macrocycles

    OpenAIRE

    Choi, Won Jun; Shi, Zhen-Dan; Worthy, Karen M.; Bindu, Lakshman; Karki, Rajeshri G.; Nicklaus, Marc C.; Fisher, Robert J.; Burke, Terrence R

    2006-01-01

    Copper (I) promoted [3+2] Huisgen cycloaddition of azides with terminal alkynes was used to prepare triazole-containing macrocycles based on the Grb2 SH2 domain-binding motif, “Pmp-Ac6 c-Asn”, where Pmp and Ac6 c stand for 4-phosphonomethylphenylalanine and 1-aminocyclohexanecarboxylic acid, respectively. When cycloaddition reactions were conducted at 1 mM substrate concentrations cyclization of monomeric units occurred. At 2 mM substrate concentrations the predominant products were macrocycl...

  10. Novel 1,3-dipolar cycloadditions of dinitraminic acid: implications for the chemical stability of ammonium dinitramide.

    Science.gov (United States)

    Rahm, Martin; Brinck, Tore

    2008-03-20

    Density functional theory at the B3LYP/6-31+G(d,p) level and ab initio calculations at the CBS-QB3 level have been used to analyze 1,3 dipolar cycloaddition reactions of dinitraminic acid (HDN) and its proton transfer isomer (HO(O)NNNO2). It is shown that the nitro group of HDN and the -N-N=O functionality of the isomer react readily with carbon-carbon double bonds. Cycloadditions of HDN are compared with the corresponding reactions with azides and nitrile oxides as 1,3 dipoles. It is shown that the reactivities of HDN and its proton transfer isomer decrease with increasing electron withdrawing power of the substituents adjacent to the carbon-carbon double bond. In contrast, for azides and nitrile oxides, the highest reactivity is obtained with dipolarophiles with strongly electron withdrawing substituents. The observed reactivity trends allow for the design of unsaturated compounds that are highly reactive toward azides and chemically inert toward dinitramides. This may be of relevance for the development of binder materials for ammonium dinitramide based propellants. PMID:18278886

  11. Blue-light activated rapid polymerization for defect-free bulk Cu(i)-catalyzed azide-alkyne cycloaddition (CuAAC) crosslinked networks.

    Science.gov (United States)

    Shete, Abhishek U; El-Zaatari, Bassil M; French, Jonathan M; Kloxin, Christopher J

    2016-08-18

    A visible-light (470 nm wavelength) sensitive Type II photoinitiator system is developed for bulk Cu(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions in crosslinked networks. The accelerated photopolymerization eliminates UV-mediated azide decomposition allowing for the formation of defect-free glassy networks which exhibit a narrow glass transition temperature. PMID:27499057

  12. Tandem RCM–Claisen Rearrangement–[2+2] Cycloaddition of O,O'-(But-2-en-1,4-diyl-bridged Binaphthols

    Directory of Open Access Journals (Sweden)

    Michael Abraham

    2012-12-01

    Full Text Available Attempted RCM of 2,2'-bis(allyloxy-1,1'-binaphthyl resulted in a Claisen-type rearrangement of a postulated labile dioxacyclodecine proceeding at room temperature and followed by [2+2] cycloaddition. Structures of products were confirmed by X-ray crystallography. A mechanistic rationalisation based on relative stabilities of proposed intermediates and transition states is provided.

  13. Tandem RCM–Claisen Rearrangement–[2+2] Cycloaddition of O,O'-(But-2-en-1,4-diyl)-bridged Binaphthols

    OpenAIRE

    Michael Abraham; Wolfgang Reischl; Karl A. Kirchner; Alexander Roller; Veiros, Luis F.; Michael Widhalm

    2012-01-01

    Attempted RCM of 2,2'-bis(allyloxy)-1,1'-binaphthyl resulted in a Claisen-type rearrangement of a postulated labile dioxacyclodecine proceeding at room temperature and followed by [2+2] cycloaddition. Structures of products were confirmed by X-ray crystallography. A mechanistic rationalisation based on relative stabilities of proposed intermediates and transition states is provided.

  14. Visible-light photoredox catalyzed synthesis of pyrroloisoquinolines via organocatalytic oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade with Rose Bengal

    Directory of Open Access Journals (Sweden)

    Carlos Vila

    2014-05-01

    Full Text Available Pyrrolo[2,1-a]isoquinoline alkaloids have been prepared via a visible light photoredox catalyzed oxidation/[3 + 2] cycloaddition/oxidative aromatization cascade using Rose Bengal as an organo-photocatalyst. A variety of pyrroloisoquinolines have been obtained in good yields under mild and metal-free reaction conditions.

  15. One-pot synthesis of new series 3,4,5-trisubstituted-dihydroisoxazoline derivatives via 1,3-dipolar cycloaddition of nitrile oxides with chalcones

    Indian Academy of Sciences (India)

    Raad Kasim Yhya; K M Lokanatha Rai; Ebraheem Abdu Musad

    2013-07-01

    We have synthesized a series of novel isoxazolines via 1,3-dipolar cycloaddition reaction. Aromatic aldoximes undergo oxidative-dehydrogenation with chloramine-T to give nitrile oxides, which were reacted with chalcones to afford of 3,4,5-trisubstituted 4,5-dihydroisoxazolines in a good yield.

  16. Asymmetric Domino Aza-Michael Addition/[3+2] Cycloaddition Reactions as a Versatile Approach to alpha,beta,gamma,-Triamino Acid Derivatives

    Czech Academy of Sciences Publication Activity Database

    Kapras, Vojtěch; Pohl, Radek; Císařová, I.; Jahn, Ullrich

    2014-01-01

    Roč. 16, č. 4 (2014), s. 1088-1091. ISSN 1523-7060 Institutional support: RVO:61388963 Keywords : 1,3-dipolar cycloaddition * lithium amides * aza-Michael addition * amino acids * pyrazoles Subject RIV: CC - Organic Chemistry Impact factor: 6.364, year: 2014

  17. Aprotic Heterocyclic Anion Triazolide Ionic Liquids - A New Class of Ionic Liquid Anion Accessed by the Huisgen Cycloaddition Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Robert L; Damodaran, Krishnan; Luebke, David; Nulwala, Hunaid

    2013-06-01

    The triazole core is a highly versatile heterocyclic ring which can be accessed easily with the Cu(I)-catalyzed Huisgen cycloaddition reaction. Herein we present the preparation of ionic liquids that incorporate a 1,2,3-triazolide anion. These ionic liquids were prepared by a facile procedure utilizing a base-labile pivaloylmethyl group at the 1-position, which can act as precursors to 1H- 4-substituted 1,2,3-triazole. These triazoles were then subsequently converted into ionic liquids after deprotonation using an appropriate ionic liquid cation hydroxide. The densities and thermal decompositions of these ionic liquids were measured. These novel ionic liquids have potential applications in gas separations and in metal-free catalysis.

  18. Synthesis with Perfect Atom Economy: Generation of Furan Derivatives by 1,3-Dipolar Cycloaddition of Acetylenedicarboxylates at Cyclooctynes

    Directory of Open Access Journals (Sweden)

    Klaus Banert

    2014-09-01

    Full Text Available Cyclooctyne and cycloocten-5-yne undergo, at room temperature, a 1,3-dipolar cycloaddition with dialkyl acetylenedicarboxylates 1a,b to generate furan-derived short-lived intermediates 2, which can be trapped by two additional equivalents of 1a,b or alternatively by methanol, phenol, water or aldehydes to yield polycyclic products 3b–d, orthoesters 4a–c, ketones 5 or epoxides 6a,b, respectively. Treatment of bis(trimethylsilyl acetylenedicarboxylate (1c with cyclooctyne leads to the ketone 7 via retro-Brook rearrangement of the dipolar intermediate 2c. In all cases, the products are formed with perfect atom economy.

  19. Chemoselective Switch in the Asymmetric Organocatalysis of 5 H -Oxazol-4-ones and N -Itaconimides: Addition-Protonation or [4+2] Cycloaddition

    KAUST Repository

    Zhu, Bo

    2015-12-09

    © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. We report a synthetic strategy for a chemoselective switch and a diastereo-divergent approach for the asymmetric reaction of 5H-oxazol-4-ones and N-itaconimides catalyzed by L-tert-leucine-derived tertiary amine-urea compounds. The reaction was modulated to harness either tandem conjugate addition-protonation or [4+2] cycloaddition as major product with excellent enantio- and diastereoselectivities. Subjecting the enantio-enriched cycloaddition products to a basic silica gel reagent yields the diastereomer vis-à-vis the product directly obtained under conditions for addition-protonation, thus opening a diastereo-divergent route for creating 1,3-tertiary-hetero-quaternary stereocenters. Quantum chemical studies further provide stereochemical analysis for the [4+2] process and a plausible mechanism for this chemoselective switch is proposed.

  20. Mechanism and regioselectivity of 1,3-dipolar cycloaddition reactions of sulphur-centred dipoles with furan-2,3-dione: A theoretical study using DFT

    Indian Academy of Sciences (India)

    Saeed Reza Emamian; Safa Ali-Asgari; Ehsan Zahedi

    2014-01-01

    The mechanism and regioselectivity of 1,3-dipolar cycloaddition reactions of sulphur-centred 1,3-dipoles including thiocarbonyl S-imide (D1), thiocarbonyl S-oxide (D2) and thiocarbonyl S-sulphide (D3) with an electron-deficient dipolarophile, furan-2,3-dione (DPh), were studied in the light of some theoretical approaches, namely, activation energy, density functional theory (DFT) reactivity indices and Houk’s rule based on the frontier molecular orbital (FMO) theory at the B3LYP/6-311++G∗∗ level. The present analysis reveals that the cycloaddition reactions under study can be classified in the normal electron demand category. An excellent agreement was observed between the kinetic results and the electronic approaches; in fact, maximum hardness principle (MHP), Chattaraj’s polar model, Houk’s rule and the Gazquez-Mendez rule confirm the resultant regioselectivity based on the calculated activation energies.

  1. Intramolecular photochemical cycloaddition of a vinylogous imide. Crystal and molecular structure of a tetracyclic C17H25O2N product

    International Nuclear Information System (INIS)

    Pyrex-filtered irradiation of N-acetyl-3-(N-cyclohexenylmethyl)amino-5,5-dimethyl-2-cyclohexen-1-one (1) provides an acyl migration product and an intramolecular cycloaddition product. The cycloaddition reaction was shown to be thermally reversible. The structure of the tetracyclic product was inferred from chemical and spectroscopic data, and the stereochemistry was fully defined via X-ray crystal-structure analysis. Crystal data (from single-crystal diffractometry, Mo Kα1,lambda = 0.70926 A, at T = 20 +- 10C): a = 20.815 (8), b = 10.875 (2), c = 6.625 (1) A; P212121, Z = 4; d/sub c/ = 1.218 and d/sub o/ = 1.19 g cm-3 by flotation in NaBr solutions; f(000) = 600. 1 figure

  2. Synthesis of novel isatin-type 5'-(4-Alkyl/Aryl-1H-1,2,3-triazoles) via 1,3-dipolar cycloaddition reactions

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Bianca N. M.; Silva, Barbara V.; Pinto, Angelo C., E-mail: biancanascimento@iq.ufrj.br [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica; Silva, Fernando C.; Gonzaga, Daniel T. G.; Ferreira, Vitor F. [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Instituto de Quimica

    2013-02-15

    Isatin and 1H-1,2,3-triazoles are two classes of compounds with great prominence in organic synthesis and medicinal chemistry as they are heterocycle nuclei with a high reactivity allowing to obtain several compounds with important biological properties. Herein, the synthesis of novel 5'-(4-alquil/aril-1H-1,2,3-triazole)-isatin via reaction of 1,3-dipolar cycloaddition catalyzed by acetic acid is reported. (author)

  3. Asymmetric α,γ-Regioselective [3 + 3] Formal Cycloadditions of α,β-Unsaturated Aldehydes via Cascade Dienamine-Dienamine Catalysis.

    Science.gov (United States)

    Xiao, Wei; Yin, Xiang; Zhou, Zhi; Du, Wei; Chen, Ying-Chun

    2016-01-01

    Asymmetric α,γ-regioselective [3 + 3] formal cycloadditions of α,β-unsaturated aldehydes and 2-nitroallylic acetates have been developed for the first time. These reactions proceeded through a domino Michael addition-Michael addition sequence via an unusual cascade dienamine-dienamine catalysis of a chiral secondary amine, and multifunctional cyclohexene derivatives were generally constructed in moderate yields with excellent stereoselectivity after simple treatment with K2CO3. PMID:26653774

  4. CuO-promoted construction of N-2-aryl-substituted-1,2,3-triazoles via azide-chalcone oxidative cycloaddition and post-triazole arylation.

    Science.gov (United States)

    Zhang, Yuanqing; Li, Xiaolong; Li, Jihui; Chen, Jinying; Meng, Xu; Zhao, Mingming; Chen, Baohua

    2012-01-01

    An efficient one-pot three-component stepwise approach for the synthesis of N-2-aryl-substituted-1,2,3-triazoles has been developed. By using this azide-chalcone oxidative cycloaddition and post-triazole arylation, a series of N-2-aryl-substituted-1,2,3-triazoles are readily prepared under mild conditions in excellent yields and high regioselectivity. Both the catalyst and substrates are readily available. PMID:22133007

  5. Traceless Azido Linker for the Solid-Phase Synthesis of NH-1,2,3-Triazoles via Cu-Catalyzed Azide-Alkyne Cycloaddition Reactions

    DEFF Research Database (Denmark)

    Cohrt, Anders Emil; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

    2010-01-01

    A broadly useful acid-labile traceless azido linker for the solid-phase synthesis of NH-1,2,3-triazoles is presented. A variety of alkynes were efficiently immobilized on a range of polymeric supports by Cu(I)-mediated azide-alkyne cycloadditions. Supported triazoles showed excellent compatibilit...... with subsequent peptide chemistry. Release of pure material (typically >95%) from the solid support was readily achieved by treatment with aqueous TFA....

  6. INVESTIGATION INTO THE REGIOCHEMISTRY OF SOME PYRAZOLES DERIVED FROM 1, 3-DIPOLAR CYCLOADDITION OF ACRYLONITRILE WITH SOME NITRILIMINES: THEORETICAL AND EXPERIMENTAL STUDIES

    OpenAIRE

    FARID MOEINPOUR; MEHDI BAKAVOLI; ABOLGHASEM DAVOODNIA; ALI MORSALI

    2011-01-01

    1,3-dipolar cycloaddition between acrylonitrile and two N-(4-substituted)phenyl-C-(4-chlorophenyl)nitrilimines which were generated in situ afforded the new pyrazoles. The regiochemistry and reactivity of these reactions has been investigated on the basis of density functional theory (DFT) -based reactivity indexes and activation energy calculations. The theoretical 13C NMR chemical shifts of the cycloadducts which were obtained by GIAO method were comparable with the observed values.

  7. Lewis acid-catalyzed intramolecular [3+2] cycloaddition of cyclopropane 1,1-diesters with alkynes for the synthesis of cyclopenta[c]chromene skeletons.

    Science.gov (United States)

    Xia, Xiao-Feng; Song, Xian-Rong; Liu, Xue-Yuan; Liang, Yong-Min

    2012-06-01

    An efficient method to construct cyclopenta[c]chromene skeletons by Lewis acid-catalyzed intramolecular [3+2] cycloaddition of cyclopropane 1,1-diesters with alkynes is presented. Two new fused cycles can be formed in one step in moderate to excellent yields (up to 94 %), and the products can be converted into bioactive barbituric acid derivatives (1) under simple reaction conditions. PMID:22488826

  8. An Enantioselective Approach to the Hetisine Alkaloids. Synthesis of the 3-Methyl-1-aza-tricyclo[5.2.1.03,8]decane Core via Intramolecular Dipolar Cycloaddition

    OpenAIRE

    Peese, Kevin M.; Gin, David Y.

    2005-01-01

    An efficient, enantioselective approach to the hetisine class of the C20-diterpenoid alkaloids is described. The strategy involves an intramolecular oxidopyridinium dipolar cycloaddition as the key transformation, in which simultaneous formation of the C5-C6 and C10-C20 bonds in the 3-methyl-1-aza-tricyclo[5.2.1.03,8]decane core of the hetisine alkaloids is effected.

  9. Ring Expansion of Cyclic 1,2-Diols to form Medium Sized Rings via Ruthenium Catalyzed Transfer Hydrogenative [4+2] Cycloaddition

    OpenAIRE

    Kasun, Zachary A.; Geary, Laina M.; Krische, Michael J.

    2014-01-01

    A new method for the ring expansion of cyclic diols is described. Using improved conditions for the ruthenium(0) catalyzed cycloaddition of cyclic 1,2-diols with 1,3-dienes, fused [n.4.0] bicycles 3a–3r (n = 3–6) are formed, which upon exposure to iodosobenzene diacetate engage in oxidative cleavage to form the 9–12 membered rings 4a–4r.

  10. 1,3-Dipolar Cycloaddition Reactions of 1-(4-Phenylphenacyl)-1,10-phenanthrolinium N-Ylide with Activated Alkynes and Alkenes

    OpenAIRE

    A. Badoiu; Caproiu, M. T.; Draghici, C.; Caira, M. R.; Dumitrascu, F.

    2005-01-01

    The 3 2 cycloaddition reaction of 1-(4-phenylphenacyl)-1,10-phenanthrolinium ylide with activated alkynes gave pyrrolo[1,2- 4a][1,10]phenanthrolines 6a-d. The "one pot" synthesis of 6a,b,d from 4, activatedalkenes, Et3N and tetrakis-pyridine cobalt (II) dichromate (TPCD) is described. Thehelical chirality of pyrrolophenanthrolines 6b-d was put in evidence by NMRspectroscopy.

  11. Comparative analysis of Cu (I)-catalyzed alkyne-azide cycloaddition (CuAAC) and strain-promoted alkyne-azide cycloaddition (SPAAC) in O-GlcNAc proteomics.

    Science.gov (United States)

    Li, Shanshan; Zhu, He; Wang, Jiajia; Wang, Xiaomin; Li, Xu; Ma, Cheng; Wen, Liuqing; Yu, Bingchen; Wang, Yuehua; Li, Jing; Wang, Peng George

    2016-06-01

    O-linked β-N-acetylglucosamine (O-GlcNAc) is emerging as an essential protein post-translational modification in a range of organisms. It is involved in various cellular processes such as nutrient sensing, protein degradation, gene expression, and is associated with many human diseases. Despite its importance, identifying O-GlcNAcylated proteins is a major challenge in proteomics. Here, using peracetylated N-azidoacetylglucosamine (Ac4 GlcNAz) as a bioorthogonal chemical handle, we described a gel-based mass spectrometry method for the identification of proteins with O-GlcNAc modification in A549 cells. In addition, we made a labeling efficiency comparison between two modes of azide-alkyne bioorthogonal reactions in click chemistry: copper-catalyzed azide-alkyne cycloaddition (CuAAC) with Biotin-Diazo-Alkyne and stain-promoted azide-alkyne cycloaddition (SPAAC) with Biotin-DIBO-Alkyne. After conjugation with click chemistry in vitro and enrichment via streptavidin resin, proteins with O-GlcNAc modification were separated by SDS-PAGE and identified with mass spectrometry. Proteomics data analysis revealed that 229 putative O-GlcNAc modified proteins were identified with Biotin-Diazo-Alkyne conjugated sample and 188 proteins with Biotin-DIBO-Alkyne conjugated sample, among which 114 proteins were overlapping. Interestingly, 74 proteins identified from Biotin-Diazo-Alkyne conjugates and 46 verified proteins from Biotin-DIBO-Alkyne conjugates could be found in the O-GlcNAc modified proteins database dbOGAP (http://cbsb.lombardi.georgetown.edu/hulab/OGAP.html). These results suggested that CuAAC with Biotin-Diazo-Alkyne represented a more powerful method in proteomics with higher protein identification and better accuracy compared to SPAAC. The proteomics credibility was also confirmed by the molecular function and cell component gene ontology (GO). Together, the method we reported here combining metabolic labeling, click chemistry, affinity-based enrichment, SDS

  12. Dearomative [2 + 2] Cycloaddition and Formal C-H Insertion Reaction of o-Carboryne with Indoles: Synthesis of Carborane-Functionalized Heterocycles.

    Science.gov (United States)

    Zhao, Da; Zhang, Jiji; Xie, Zuowei

    2015-07-29

    o-Carboryne (1,2-dehydro-o-carborane) is a very useful synthon for the synthesis of a variety of carborane-functionalized heterocycles. Reaction of o-carboryne with N-protected indoles gave carborane-fused indolines if the protecting group was TMS via dearomative [2 + 2] cycloaddition or carboranyl indoles for N-alkyl ones through formal C-H insertion reaction. For N-aryl indoles, both reactions were observed, giving two products, in which the product ratio was dependent upon the nature of the substituents on the aryl rings. In general, electron-withdrawing substituents favor [2 + 2] cycloaddition, whereas electron-donating substituents promote a formal C-H insertion pathway. This reaction is also compatible with other heteroaromatics. Thus, a stepwise reaction mechanism was proposed to account for the experimental observations. These protocols offer general and efficient methods for the preparation of carborane-functionalized indoles and indolines as well as other heterocycles. The observed dearomative [2 + 2] cycloaddition represents the first example of indoles to undergo such reaction in the absence of transition metals or without UV irradiation. All new compounds were fully characterized by (1)H, (13)C, and (11)B NMR spectroscopy as well as HRMS spectrometry. Some were further confirmed by single-crystal X-ray analyses. PMID:26160111

  13. A highly active and magnetically recoverable tris(triazolyl)-Cu(I) catalyst for alkyne-azide cycloaddition reactions.

    Science.gov (United States)

    Wang, Dong; Etienne, Laetitia; Echeverria, María; Moya, Sergio; Astruc, Didier

    2014-04-01

    Nanoparticle-supported tris(triazolyl)-CuBr, with a diameter of approximately 25 nm measured by TEM spectroscopy, has been easily prepared, and its catalytic activity was evaluated in the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. In initial experiments, 0.5 mol % loading successfully promoted the CuAAC reaction between benzyl azide and phenylacetylene, in water at room temperature (25 °C). During this process, the iron oxide nanoparticle-supported tris(triazolyl)-CuBr displayed good monodispersity, excellent recoverability, and outstanding reusability. Indeed, it was simply collected and separated from the reaction medium by using an external magnet, then used for another five catalytic cycles without significant loss of catalytic activity. Inductively coupled plasma (ICP) analysis for the first cycle revealed that the amount of copper leached from the catalyst into the reaction medium is negligible (1.5 ppm). The substrate scope has been examined, and it was found that the procedure can be successfully extended to various organic azides and alkynes and can also be applied to the one-pot synthesis of triazoles, through a cascade reaction involving benzyl bromides, alkynes, and sodium azide. In addition, the catalyst was shown to be an efficient CuAAC catalyst for the synthesis of allyl- and TEG-ended (TEG=triethylene glycol) 27-branch dendrimers. PMID:24574335

  14. Lateral extension of π conjugation along the bay regions of bisanthene through a diels-alder cycloaddition reaction

    KAUST Repository

    Li, Jinling

    2011-11-14

    Diels-Alder cycloaddition reactions at the bay regions of bisanthene (1) with dienophiles such as 1,4-naphthoquinone have been investigated. The products were submitted to nucleophilic addition followed by reductive aromatization reactions to afford the laterally extended bisanthene derivatives 2 and 3. Attempted synthesis of a larger expanded bisanthene 4 revealed an unexpected hydrogenation reaction at the last reductive aromatization step. Unusual Michael addition was observed on quinone 14, which was obtained by Diels-Alder reaction between 1 and 1,4-anthraquinone. Compounds 1-3 exhibited near-infrared (NIR) absorption and emission with high-to-moderate fluorescent quantum yields. Their structures and absorption spectra were studied by density function theory and non-planar twisted structures were calculated for 2 and 3. All compounds showed amphoteric redox behavior with multiple oxidation/reduction waves. Oxidative titration with SbCl 5 gave stable radical cations, and the process was followed by UV/Vis/NIR spectroscopic measurements. Their photostability was measured and correlated to their different geometries and electronic structures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Concerted, highly asynchronous, enzyme-catalyzed [4 + 2] cycloaddition in the biosynthesis of spinosyn A; computational evidence.

    Science.gov (United States)

    Hess, B Andes; Smentek, Lidia

    2012-10-01

    A theoretical study has been carried out on model systems to study a recently reported, (Nature, 2011, 473, 109) biosynthetic, [4 + 2] cycloaddition catalyzed by a stand-alone enzyme (the cyclase SpnF). It was suggested in this paper that SpnF is the first known example of a Diels-Alderase (DA). In the present study, for a model system of the substrate a transition structure was found with density functional calculations (DFT). In addition, the intrinsic reaction coordinate calculations indicated that the transition structure is that of a concerted, but highly asynchronous, DA reaction. Based on the DFT and Møller-Plesset second order calculations the activation energy was estimated to be about 15 kcal mol(-1). The results of a natural population analysis indicated that there is significant charge transfer in the transition state, and it is proposed that possibly the enzyme plays a dual role of not only folding the substrate into the proper conformation for the DA reaction to occur, but also lowering its activation energy by stabilization of the highly polarized transition structure. PMID:22885939

  16. Triphenylene discotic liquid crystal trimers synthesized by Co2(CO8-catalyzed terminal alkyne [2 + 2 + 2] cycloaddition

    Directory of Open Access Journals (Sweden)

    Bin Han

    2013-12-01

    Full Text Available The synthesis of star-shaped discotic liquid crystal trimers using Co2(CO8-catalyzed terminal alkyne [2 + 2 + 2] cycloaddition reaction is reported. The trimers consist of three triphenylene discotic units linked to a central 1,2,4-trisubstituted benzene ring via flexible spacers. The trimers were synthesized in the yields up to 70% by mixing the monomers with 10 mol % of Co2(CO8 as the catalyst in refluxing 1,4-dioxane. The liquid crystalline properties were investigated by using polarizing optical microscopy (POM, differential scanning calorimetry (DSC and X-ray diffraction (XRD. Trimer 4 with an ester connecting group and a longer spacer exhibited a rectangular columnar mesophase, while 5b and 5c possessing an ether linkage and a shorter spacer display a hexagonal columnar mesophase. The connecting functional group and the length of the flexible spacer between the central benzene ring and the triphenylene units have pivotal influence on the mesomorphism.

  17. 1,3,4-Thiadiazoles of pharmacological interest: Recent trends in their synthesis via tandem 1,3-dipolar cycloaddition: Review

    Directory of Open Access Journals (Sweden)

    Ahmad S. Shawali

    2014-01-01

    Full Text Available This review article presents a survey of the utility of a new synthetic strategy for 1,3,4-thiadiazole derivatives based on reactions of nitrilimines with various functionalized sulfur dipolarophiles which proceed via tandem in situ 1,3-dipolar cycloaddition and β-elimination of simple molecule from the initially formed cycloadduct. The biological activities of some of the compounds prepared by such a strategy are pointed out. Only the literature reports within the period from 2000 to mid 2012 are covered.

  18. Assessment of the Full Compatibility of Copper(I)-Catalyzed Alkyne-Azide Cycloaddition and Oxime Click Reactions for bis-Labelling of Oligonucleotides

    OpenAIRE

    Estalayo-Adriàn, Sandra; Lartia, Rémy; Meyer, Albert; Vasseur, Jean-Jacques; Morvan, François; Defrancq, Eric

    2014-01-01

    The conjugation of oligonucleotides with reporters is of great interest for improving their intrinsic properties or endowing new ones. In this context, we report herein a new procedure for the bis-labelling of oligonucleotides through oxime ligation (Click-O) and copper(I)-catalyzed alkyne–azide cycloaddition (Click-H). 5′-Azido and 3′-aldehyde precursors were incorporated into oligonucleotides, and subsequent coupling reactions through Click-O and Click-H (or vice versa) were successfully ac...

  19. Synthesis of bi- and bis-1,2,3-triazoles by copper-catalyzed Huisgen cycloaddition: A family of valuable products by click chemistry

    OpenAIRE

    Zhan-Jiang Zheng; Ding Wang; Zheng Xu; Li-Wen Xu

    2015-01-01

    The Cu(I)-catalyzed azide-alkyne cycloaddition reaction, also known as click chemistry, has become a useful tool for the facile formation of 1,2,3-triazoles. Specifically, the utility of this reaction has been demonstrated by the synthesis of structurally diverse bi- and bis-1,2,3-triazoles. The present review focuses on the synthesis of such bi- and bistriazoles and the importance of using copper-promoted click chemistry (CuAAC) for such transformations. In addition, the application of bitri...

  20. Synthesis of bi- and bis-1,2,3-triazoles by copper-catalyzed Huisgen cycloaddition: A family of valuable products by click chemistry

    Science.gov (United States)

    Wang, Ding; Xu, Zheng

    2015-01-01

    Summary The Cu(I)-catalyzed azide-alkyne cycloaddition reaction, also known as click chemistry, has become a useful tool for the facile formation of 1,2,3-triazoles. Specifically, the utility of this reaction has been demonstrated by the synthesis of structurally diverse bi- and bis-1,2,3-triazoles. The present review focuses on the synthesis of such bi- and bistriazoles and the importance of using copper-promoted click chemistry (CuAAC) for such transformations. In addition, the application of bitriazoles and the related CuAAAC reaction in different fields, including medicinal chemistry, coordination chemistry, biochemistry, and supramolecular chemistry, have been highlighted. PMID:26734102

  1. A New Multicomponent Multicatalyst Reaction (MC)(2)R: Chemoselective Cycloaddition and Latent Catalyst Activation for the Synthesis of Fully Substituted 1,2,3-Triazoles.

    Science.gov (United States)

    Yamamoto, Kosuke; Bruun, Theodora; Kim, Jung Yun; Zhang, Lei; Lautens, Mark

    2016-06-01

    A multicomponent multicatalyst reaction (MC)(2)R for constructing fully substituted 1,2,3-triazoles is reported. An application of chemoselectivity and latent catalysis in a sequence of multicatalytic reactions confers control over a number of undesired processes, where all of the reagents coexist in the same reaction vessel. The sequence of a chemoselective copper-catalyzed azide alkyne cycloaddition followed by a palladium/copper-catalyzed Sonogashira cross-coupling afforded 1,2,3-triazoles regioselectively with good to high yields and a broad scope. PMID:27213631

  2. A Novel One-Pot Green Synthesis of Dispirooxindolo-pyrrolidines via 1,3-Dipolar Cycloaddition Reactions of Azomethine Ylides

    Directory of Open Access Journals (Sweden)

    Abdulrahman I. Almansour

    2015-01-01

    Full Text Available A facile synthesis of dispirooxindolopyrrolidines has been accomplished via a one-pot three component 1,3-dipolar cycloaddition reaction. The reaction of azomethine ylides generated in situ from L-phenylalanine and substituted isatins with a series of unusual (E-2-oxoindolino-3-ylidene acetophenone dipolarophiles in the ionic liquid 1-butyl-3-methylimidazolium bromide [bmim]BF4, furnished the cycloadducts in good yields, with the regioisomers 5a–f being obtained with high selectivity. Furthermore, the recyclability of [bmim]BF4, up to five times, was also investigated.

  3. Synthesis of bi- and bis-1,2,3-triazoles by copper-catalyzed Huisgen cycloaddition: A family of valuable products by click chemistry

    Directory of Open Access Journals (Sweden)

    Zhan-Jiang Zheng

    2015-12-01

    Full Text Available The Cu(I-catalyzed azide-alkyne cycloaddition reaction, also known as click chemistry, has become a useful tool for the facile formation of 1,2,3-triazoles. Specifically, the utility of this reaction has been demonstrated by the synthesis of structurally diverse bi- and bis-1,2,3-triazoles. The present review focuses on the synthesis of such bi- and bistriazoles and the importance of using copper-promoted click chemistry (CuAAC for such transformations. In addition, the application of bitriazoles and the related CuAAAC reaction in different fields, including medicinal chemistry, coordination chemistry, biochemistry, and supramolecular chemistry, have been highlighted.

  4. Convergent Synthesis of 2H-Chromenes – a Formal [3+3] Cycloaddition by a One-pot, Three-Step Cascade

    OpenAIRE

    Parker, Kathlyn A.; Thomas L. Mindt

    2011-01-01

    In cases in which the palladium-catalyzed coupling of a bromoquinone with a vinyl stannane affords a vinyl quinone that enolizes, the resulting ortho-quinone methide undergoes an oxa-6π electrocyclization. Enolization is promoted by the presence of a polar additive. The net conversion is a formal [3+3] cycloaddition that gives 2H-chromenes. Because the first two steps of the cascade are catalyzed, the overall conversion is an example of multicatalysis. Yields for the optimized, one-pot protoc...

  5. Synthesis and photochemistry of styryl substituted annelated furan derivatives. IV. Concentration directed intra- and/or intermolecular [2+2] cycloaddition

    OpenAIRE

    Škorić, Irena; Marinić, Željko; Sindler-Kulyk, Marija

    2004-01-01

    New cyclobutane derivatives have been synthesized by intermolecular photochemical [2+2] ethene-ethene "head-to-head" (9a,b) and "head-to-tail" (10a,b-11a,b) as well as [2+2] ethene-furan (12a,b) cycloaddition from 2-[2-(2-vinylphenyl)ethenyl]benzo[b]furan (2a) and 2-[2-(2-methylphenyl)ethenyl]benzo[b]furan (2b), respectively. All compounds were isolated and characterized by spectroscopic methods. Under the benzene solution irradiation of 5 x 10(-1) 1 mol dm(-3) concentration and higher, 2-[2-...

  6. Synthesis of novel triazoles bearing 1,2,4-oxadiazole and phenylsulfonyl groups by 1,3-dipolar cycloaddition of some organic azides and their biological activities

    OpenAIRE

    DÜRÜST, Yaşar; KARAKUŞ, Hamza; YAVUZ, Muhsine Zeynep; GEPDİREMEN, Ali Akçahan

    2014-01-01

    1,3-Dipolar cycloaddition of 5-azidomethyl-3-p-substituted phenyl-1,2,4-oxadiazoles to phenyl vinyl sulfone and bismaleimide gives rise straightforwardly to 1-((3-(p-substituted) phenyl-1,2,4-oxadiazol-5-yl)methyl)-4-(phenylsul\\-fonyl)-4,5-dihydro-1H-1,2,3-triazoles and bisdihydropyrrolo[3,4-d][1,2,3]triazole-4,6(3aH,5H)-diones. The structures of the new cycloadducts were elucidated by means of IR, NMR (1H, 13C, 2D), mass spectra, and physical characteristics (mp and Rf values). In addition, ...

  7. [2n2π + 2n2π] Cycloadditions: an alternative to forbidden [4π + 4π] processes. The case of nitrone dimerization

    OpenAIRE

    Roca-López, David; Tejero, Tomás; Caramella, Pierluigi; Merino, Pedro

    2014-01-01

    A theoretical study based on (U)M06-2X/cc-pVTZ calculations has been used to investigate the [3 + 3] thermal dimerization of nitrones to 1,4,2,5-dioxadiazinanes in both the gas phase and in dichloromethane solution. Calculations suggest that dimerization of nitrones takes place through a concerted mechanism involving a formal disallowed [4π + 4π] cycloaddition with a free energy barrier of 30.8 kcal mol−1. The corresponding diradical and zwitterionic stepwise mechanisms have also been studied...

  8. A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives

    Directory of Open Access Journals (Sweden)

    Hamzehloueian Mahshid

    2014-01-01

    Full Text Available The present study reports a systematic computational analysis of the two possible pathways, fused and bridged, for an intramolecular hetero Diels-Alder (IMHDA and an intramolecular 1,3-dipolar cycloaddition (IMDCA of 2-vinyloxybenzaldehyde derivatives. The potential energy surface analysis for both reactions is in agreement with experimental observations. The activation energies associated with the two regioisomeric channels in IMHDA reaction show that the bridged product is favored, although in IMDCA, the most stable TS results the fused product. The global electronic properties of fragments within each molecule were studied to discuss the reactivity patterns and charge transfer direction in the intramolecular processes. The asynchronicity of the bond formation and aromaticity of the optimized TSs in the Diels-Alder reaction as well as cycloaddition reaction were evaluated. Finally, 1H NMR chemical shifts of the possible regioisomers have been calculated using the GIAO method which of the most stable products are in agreement with the experimental data in the both reaction.

  9. Theoretical investigation of the mechanism for the cycloaddition of CO2 to epoxides catalyzed by a magnesium(II) porphyrin complex.

    Science.gov (United States)

    Wang, Qin; Guo, Cai-Hong; Jia, Jianfeng; Wu, Hai-Shun

    2015-07-01

    The cycloaddition of CO2 to epoxides, catalyzed by Mg(TPP)/TBAI (TPP = tetraphenylporphyrin; TBAI = tetrabutylammonium iodide), was investigated using DFT methods. Epoxides with various substituents were studied to explore steric and electronic effects on the reaction mechanism. Computational results show that the cycloaddition proceeds according to a much easier mechanism in the presence of Mg(TPP) and TBAI than the mechanism that takes place when Mg(TPP) is used as the catalyst. A preference for the epoxide ring-opening to occur at the methine (Cα) or methylene (Cβ) carbon was noted. The ring-closing step leading to the formation of a five-membered carbonate is predicted to determine the reaction rate. For alkyl-substituted epoxides, the β pathway is favorable since steric factors are dominant; for epoxides with a strongly electron-donating group and styrene oxide, the reaction is mainly controlled by electronic factors and proceeds along the α pathway. When the epoxide has a strongly electron-withdrawing group (CF3), both steric and electronic effects play important roles. The calculated reactivity of epoxides with CO2 catalyzed by Mg(TPP)/TBAI is in good agreement with that observed experimentally. PMID:26113116

  10. The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents

    Directory of Open Access Journals (Sweden)

    Martha Mojica

    2016-02-01

    Full Text Available The Diels-Alder (DA reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs. The density functional theory (DFT B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1 and pentacyclopentacorannulene (pristine hemifullerene 2, could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH2, OMe, OH, Me, i-Pr and electron-withdrawing groups (F, COOH, CF3, CHO, CN, NO2. The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO2 substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

  11. 1, 3-Dipolar cycloaddition reactions: Synthesis of 5-benzyl-1-(2',4'-dibromophenyl)-3-(4"-substituted phenyl)-3a,4,6,6a-tetrahydro-1, 5-pyrrolo[3,4-]pyrazole-4,6-dione derivatives

    Indian Academy of Sciences (India)

    Manpreet Kaur; Baldev Singh; Baljit Singh

    2013-11-01

    1,3-Dipolar cycloaddition of nitrilimines 3 with -benzyl maleimide 4 has provided 5-benzyl-1-(2',4'-dibromophenyl)-3-(4"-substituted phenyl)-3a,4,6,6a-tetrahydro-1,5-pyrrolo[3,4-]pyrazole-4,6-dione derivatives 5 in excellent yield as the only isomer through a concerted pathway.

  12. Alkylation and 1,3-Dipolar Cycloaddition of 6-Styryl-4,5-dihydro-2H-pyridazin-3-one: Synthesis of Novel N-Substituted Pyridazinones and Triazolo[4,3-b]pyridazinones

    OpenAIRE

    José A. S. Cavaleiro; Maria A.F. Faustino; Neves, Maria G. P. M. S.; El Mostapha Rakib; Hanan Sekkak; Souad Mojahidi; Hafid Zouihri

    2013-01-01

    Some new N-substituted pyridazinones and triazolo[4,3-b]pyridazinones were synthesized, respectively, by simple alkylation and 1,3-dipolar cycloaddition of pyridazin-3-one with nitrile imines. The regioselectivity of the reactions was ascertained by 1H, 13C NMR spectroscopy and X-ray diffraction of the synthesized compounds.

  13. Cu-MCM-41 nanoparticles: An efficient catalyst for the synthesis of 5-substituted 1-tetrazoles via [3+2] cycloaddition reaction of nitriles and sodium azide

    Indian Academy of Sciences (India)

    Mohammad Abdollahi-Alibeik; Ali Moaddeli

    2016-01-01

    [3+2] cycloaddition reaction of various types of nitriles and sodium azide (NaN3) were studied in the presence of nano-sized Cu-MCM-41 as an efficient recoverable heterogeneous catalyst. Nano-sized Cu-MCM-41 mesoporous molecular sieves with various Si/Cu molar ratios were synthesized by direct insertion of metal ions at room temperature. The textural properties of the materials have been studied by means of XRD, FTIR, SEM and TEM techniques. Catalytic behavior of Cu-MCM-41 was also investigated by pyridine absorption and potentiometric titration. The reactions data verified characterization results and show that Cu-MCM-41 with Si/Cu molar ratio of 20 has considerably better catalytic activity compared to the other molar ratios. To investigate reusability, the catalyst was recovered by simple filtration and reused for several cycles with consistent activity.

  14. Application of the Huisgen cycloaddition and 'click' reaction toward various 1,2,3-triazoles as HIV non-nucleoside reverse transcriptase inhibitors.

    Science.gov (United States)

    Pribut, Nicole; Veale, Clinton G L; Basson, Adriaan E; van Otterlo, Willem A L; Pelly, Stephen C

    2016-08-01

    The development of novel anti-HIV agents remains an important medicinal chemistry challenge given that no cure for the disease is imminent, and the continued use of current NNRTIs inevitably leads to problems associated with resistance. Inspired by the pyrazole-containing NNRTI lersivirine (LSV), we embarked upon a study to establish whether 1,2,3-triazole heterocycles could be used as a new scaffold for the creation of novel NNRTIs. An especially attractive feature of triazoles used for this purpose is the versatility in accessing variously functionalised systems using either the thermally regulated Huisgen cycloaddition, or the related 'click' reaction. Employing three alternative forms of these reactions, we were able to synthesise a range of triazole compounds and evaluate their efficacy in a phenotypic HIV assay. To our astonishment, even compounds closely mimicking LSV were only moderately effective against HIV. PMID:27287366

  15. Theoretical insights into the cycloaddition reaction mechanism between ketenimine and methyleneimine: An alternative approach to the formation of pyrazole and imidazole

    Indian Academy of Sciences (India)

    Nana Wang; Xiaojun Tan; Weihua Wang; Fangfang Wang; Ping Li

    2016-02-01

    The cycloaddition reaction mechanism between interstellar molecules, ketenimine and methyleneimine, has been systematically investigated employing the second-order Møller-Plesset perturbation theory (MP2) method in order to better understand the reactivity of nitrogenous cumulene ketenimine with the C=N double bond compound methyleneimine. Geometry optimizations and vibrational analyses have been performed for the stationary points on the potential energy surfaces of the system. Calculations show that five-membered cyclic carbene intermediates could be produced through pericyclic reaction processes between ketenimine and methyleneimine. Through the subsequent hydrogen transfer processes, carbene intermediates can be isomerized to the pyrazole and imidazole compounds, respectively. The present study is helpful to understand the formation of prebiotic species in interstellar space.

  16. Multistep flow synthesis of vinyl azides and their use in the copper-catalyzed Huisgen-type cycloaddition under inductive-heating conditions

    Directory of Open Access Journals (Sweden)

    Lukas Kupracz

    2011-10-01

    Full Text Available The multistep flow synthesis of vinyl azides and their application in the synthesis of vinyltriazoles is reported. The synthesis relies on a stable polymer-bound equivalent of iodine azide that serves to carry out 1,2-functionalization of alkenes in a telescope flow protocol. The intermediate 2-iodo azides are subjected to a DBU-mediated polymer-supported elimination step yielding vinyl azides in good yield. The third step involves the formation of vinyl triazoles by a copper-catalyzed Huisgen-"click" cycloaddition. The required heat is generated by electromagnetic induction based on copper. Copper serves both as heatable as well as catalytically active packed-bed material inside the flow reactor.

  17. Niobium(v) chloride and imidazolium bromides as efficient dual catalyst systems for the cycloaddition of carbon dioxide and propylene oxide

    KAUST Repository

    Wilhelm, Michael E.

    2014-01-01

    The application of niobium(v) chloride and several imidazolium bromides as catalyst systems for the cycloaddition of propylene oxide (PO) with carbon dioxide to propylene carbonate (PC) is reported. A set of 31 different imidazolium bromides has been synthesized with varying substituents at all five imidazolium ring atoms, of which 17 have not been reported before. The impact of different substitution patterns (steric and electronic changes and solubility in PO) at the imidazolium ring on the catalytic activity was investigated. The optimisation of the catalyst structure allows for the valorisation of carbon dioxide under mild reaction conditions with high reaction rates in very good yield and selectivity for PC. This journal is © the Partner Organisations 2014.

  18. Niobium(v) chloride and imidazolium bromides as efficient dual catalyst systems for the cycloaddition of carbon dioxide and propylene oxide

    KAUST Repository

    Wilhelm, Michael E.

    2014-02-19

    The application of niobium(v) chloride and several imidazolium bromides as catalyst systems for the cycloaddition of propylene oxide (PO) with carbon dioxide to propylene carbonate (PC) is reported. A set of 31 different imidazolium bromides has been synthesized with varying substituents at all five imidazolium ring atoms, of which 17 have not been reported before. The impact of different substitution patterns (steric and electronic changes and solubility in PO) at the imidazolium ring on the catalytic activity was investigated. The optimisation of the catalyst structure allows for the valorisation of carbon dioxide under mild reaction conditions with high reaction rates in very good yield and selectivity for PC. This journal is © the Partner Organisations 2014.

  19. 'Clicking' on the nanoscale: 1,3-dipolar cycloaddition of terminal acetylenes on azide functionalized, nanometric surface templates with nanometer resolution

    Science.gov (United States)

    Haensch, Claudia; Hoeppener, Stephanie; Schubert, Ulrich S.

    2009-04-01

    Electro-oxidative lithography is used as a tool to create chemical nanostructures on an n-octadecyltrichlorosilane (OTS) monolayer self-assembled on silicon. The use of a bromine precursor molecule, which is exclusively assembled on these chemical templates, can be used to further functionalize the nanostructures by the site-selective generation of azide functions and performing the highly effective 1,3-dipolar cycloaddition reaction with acetylene functionalized molecules. The versatility of this reaction scheme provides the potential to integrate a large variety of functional molecules, to tailor the surface properties of the nanostructures or to anchor molecular building blocks or particles in confined, pre-defined surface areas. The results demonstrated in the present study introduce a conceivable route towards the functionalization of chemically active surface templates with high fidelity and reliability. It is demonstrated that surface features with a lateral resolution of 50 nm functionalized with propargyl alcohol can be fabricated.

  20. DFT study of the mechanism and stereoselectivity of the 1,3-dipolar cycloaddition between pyrroline-1-oxide and methyl crotonate

    Indian Academy of Sciences (India)

    Khadija Marakchi; Rachida Ghailane; Oum Kaltoum Kabbaj; Najia Komiha

    2014-01-01

    A theoretical study of the regio- and stereoselectivities of the 1,3-dipolar cycloaddition reaction between methyl crotonate and pyrroline-1-oxide has been carried out using density functional theory (DFT) at the B3LYP/6-31G(d) level of theory. The reaction has been followed by performing transition state optimization, calculations of intrinsic reaction coordinate and activation energies; the molecular mechanism of the reactions is concerted and asynchronous. The regio- and exo/endo-selectivity have been explained in terms of frontier molecular orbital interactions, local and global electrophilicity and nucleophilicity indices and an analysis of theWiberg bond indices in the transition state. The FMO analysis and DFT-based reactivity indices showed that the regioselectivity of this reaction is controlled by the HOMOdipole-LUMOdipolarophile interaction. The activation parameters indicated favoured endo approach along the meta-pathway in agreement with the experimental results.

  1. Cycloaddition reactions of 3-aryl-5-phenyl-5H,7H-thiazolo[3,4-c]oxazol-4-ium-1-olates

    OpenAIRE

    Melo, Teresa M. V. D. Pinho e; Gomes, Clara S. B.; Gonsalves, António M. d'A. Rocha; Paixão, José A; Beja, Ana M; Silva, Manuela Ramos; Veiga, Luiz Alte da

    2002-01-01

    Intermolecular 1,3-dipolar cycloaddition of (5R)- and (5S)-3,5-diphenyl-5H,7H-thiazolo[3,4-c]oxazol-4-ium-1-olates, (5R)- and (5S)-3-(p-methoxyphenyl)-5-phenyl-5H,7H-thiazolo-[3,4-c]oxazol-4-ium-1-olates with a range of dipolarophiles is described. New chiral 5-aryl-3-phenyl-1H,3H-pyrrolo[1,2-c]thiazoles with R and S configuration were obtained. The structure of methyl (3R)-3-phenyl-5-(p-methoxyphenyl)-1H,3H-pyrrolo[1,2-c]thiazole-6-carboxylate was determined by X-ray crystallography. The syn...

  2. Synthesis of Isoxazole and 1,2,3-Triazole Isoindole Derivatives via Silver- and Copper-Catalyzed 1,3-Dipolar Cycloaddition Reaction

    OpenAIRE

    Mohamed Mehdi Rammah; Wafa Gati; Hasan Mtiraoui; Mohamed El Baker Rammah; Kabula Ciamala; Michael Knorr; Yoann Rousselin; Kubicki, Marek M

    2016-01-01

    The CuI- or Ag2CO3-catalyzed [3+2] cycloaddition of propargyl-substituted dihydroisoindolin-1-one (3) with arylnitrile oxides 1a–d (Ar = Ph, p-MeC6H4, p-MeOC6H4, p-ClC6H4) produces in good yields novel 3,5-disubstituted isoxazoles 4 of the ethyl-2-benzyl-3-oxo-1-((3-arylisoxazol-5yl)methyl)-2,3-dihydro-1H-isoindole-1-carboxylate type. With aryl azides 2a–d (Ar = Ph, p-MeC6H4, p-OMeC6H4, p-ClC6H4), a series of 1,4-disubstituted 1,2,3-triazoles 6 (ethyl-2-benzyl-3-oxo-1-((1-aryl-1H-1,2,3-triazo...

  3. 'Clicking' on the nanoscale: 1,3-dipolar cycloaddition of terminal acetylenes on azide functionalized, nanometric surface templates with nanometer resolution

    International Nuclear Information System (INIS)

    Electro-oxidative lithography is used as a tool to create chemical nanostructures on an n-octadecyltrichlorosilane (OTS) monolayer self-assembled on silicon. The use of a bromine precursor molecule, which is exclusively assembled on these chemical templates, can be used to further functionalize the nanostructures by the site-selective generation of azide functions and performing the highly effective 1,3-dipolar cycloaddition reaction with acetylene functionalized molecules. The versatility of this reaction scheme provides the potential to integrate a large variety of functional molecules, to tailor the surface properties of the nanostructures or to anchor molecular building blocks or particles in confined, pre-defined surface areas. The results demonstrated in the present study introduce a conceivable route towards the functionalization of chemically active surface templates with high fidelity and reliability. It is demonstrated that surface features with a lateral resolution of 50 nm functionalized with propargyl alcohol can be fabricated.

  4. Total parenteral nutrition

    Science.gov (United States)

    ... medlineplus.gov/ency/patientinstructions/000177.htm Total parenteral nutrition To use the sharing features on this page, please enable JavaScript. Total parenteral nutrition (TPN) will help you or your child get ...

  5. Total Knee Replacement

    Science.gov (United States)

    ... following total knee replacement include unlimited walking, swimming, golf, driving, light hiking, biking, ballroom dancing, and other ... to the final success of your surgery. To learn more about the full value of total knee ...

  6. Total iron binding capacity

    Science.gov (United States)

    ... page: //medlineplus.gov/ency/article/003489.htm Total iron binding capacity To use the sharing features on this page, please enable JavaScript. Total iron binding capacity (TIBC) is a blood test to ...

  7. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available GLOBAL AP ANATOMIC TOTAL SHOULDER SYSTEM METHODIST HOSPITAL PHILADELPHIA, PA April 17, 2008 00:00:10 ANNOUNCER: ... you'll be able to watch a live global AP anatomic total shoulder surgery from Methodist Hospital ...

  8. Total well dominated trees

    DEFF Research Database (Denmark)

    Finbow, Arthur; Frendrup, Allan; Vestergaard, Preben D.

    cardinality then G is a total well dominated graph. In this paper we study composition and decomposition of total well dominated trees. By a reversible process we prove that any total well dominated tree can both be reduced to and constructed from a family of three small trees....

  9. Controversy Total War

    OpenAIRE

    Segesser, Daniel Marc

    2014-01-01

    Total war is a controversial term used in the past by politicians, publicists and military officers as well as by computer specialists and academics in the present. Since its conception by French politicians during the First World War in a time of severe crisis (1916/17), it has become a term used by historians and other academics to cover a wide array of elements when looking at wars of the past. A real total war was and is impossible. Elements of total war – total war aims, total methods of...

  10. Utilizing copper(I) catalyzed azide-alkyne Huisgen 1,3-dipolar cycloaddition for the surface modification of colloidal particles with electroactive and emissive moieties

    Science.gov (United States)

    Rungta, Parul

    " chemistry; Aqueous-phase 83 nm poly(propargyl acrylate) (PA) nanoparticles were surface-functionalized with sparingly water soluble fluorescent moieties through a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) (i.e., "click" transformation) to produce fluoroprobes with a large Stokes shift. For moieties which could not achieve extensive surface coverage on the particles utilizing a standard click transformation procedure, the presence of beta-cyclodextrin (beta-CD) during the transformation enhanced the grafting density onto the particles. For an oxadiazole containing molecule (AO), an azide-modified coumarin 6 (AD1) and a polyethylene glycol modified naphthalimide-based emitter (AD2), respectively, an 84%, 17% and 5% increase in the grafting densities were observed, when the transformation was performed in the presence of beta-CD. In contrast, a carbazolyl-containing moiety (AC) exhibited a slight retardation in the final grafting density when beta-CD was employed. Photoluminescence studies indicated that AC & AO when attached to the particles form an exciplex. An efficient energy transfer from the exciplex to the surface attached AD2 resulted in a total Stokes shift of 180 nm for the modified particles. (3) The synthesis and characterization of near-infrared (NIR) emitting particles for potential applications in cancer therapy. PA particles were surface modified through the "click" transformation of an azide-terminated indocyanine green (azICG), an NIR emitter, and poly(ethylene glycol) (azPEG) chains of various molecular weights. The placement of azICG onto the surface of the particles allowed for the chromophores to complex with bovine serum albumin (BSA) when dispersed in PBS that resulted in an enhancement of the dye emission. In addition, the inclusion of azPEG with the chromophores onto the particle surface resulted in a synergistic nine-fold enhancement of the fluorescence intensity, with azPEGs of increasing molecular weight amplifying the response

  11. Genoptraening efter total knaealloplastik

    DEFF Research Database (Denmark)

    Holm, Bente; Kehlet, Henrik

    2009-01-01

    The short- and long-term benefits of post-discharge physiotherapy regimens after total knee arthroplasty are debatable. A national survey including hospitals in Denmark that perform total knee arthroplasty showed a large variability in indication and regimen for post-knee arthroplasty rehabilitat......The short- and long-term benefits of post-discharge physiotherapy regimens after total knee arthroplasty are debatable. A national survey including hospitals in Denmark that perform total knee arthroplasty showed a large variability in indication and regimen for post-knee arthroplasty...

  12. Totalization Data Exchange (TDEX)

    Data.gov (United States)

    Social Security Administration — The Totalization Data Exchange (TDEX) process is an exchange between SSA and its foreign country partners to identify deaths of beneficiaries residing abroad. The...

  13. A versatile method for the preparation of end-functional polymers onto SiO2 nanoparticles by a combination of surface-initiated ATRP and Huisgen [3 + 2] cycloaddition

    International Nuclear Information System (INIS)

    A versatile method was developed for the chain-end functionalization of the grafted polymer chains for surface modification of nanoparticles with functionalized groups through a combination of surface-initiated atom-transfer radical polymerization (ATRP) and Huisgen [3 + 2] cycloaddition. First, the surface of SiO2 nanoparticles was modified with poly(methyl methacrylate) (PMMA) brushes via the 'grafting from' approach. The terminal bromides of PMMA-grafted SiO2 nanoparticles were then transformed into an azide function by nucleophilic substitution. These azido-terminated PMMA brushes on the nanoparticle surface were reacted with alkyne-terminated functional end group via Huisgen [3 + 2] cycloaddition. FTIR and 1H NMR spectra indicated quantitative transformation of the chain ends of PMMA brushes onto SiO2 nanoparticles into the desired functional group. And, the dispersibility of the end-functional polymer-grafted SiO2 nanoparticles was investigated with a transmission electron microscope (TEM).

  14. Acid-Mediated N-H/α,β-C(sp(3))-H Trifunctionalization of Pyrrolidine: Intermolecular [3 + 2] Cycloaddition for the Construction of 2,3-Dihydro-1H-Pyrrolizine Derivatives.

    Science.gov (United States)

    Zheng, Kai-Lu; Shu, Wen-Ming; Ma, Jun-Rui; Wu, Yan-Dong; Wu, An-Xin

    2016-08-01

    A one-pot acid-mediated reaction has been developed for the N-H/α,β-C(sp(3))-H trifunctionalization of pyrrolidine without any metallic reagents or external oxidants. This reaction involves the intermolecular [3 + 2] cycloaddition of in situ-generated azomethine ylides with acrylic esters to provide facile access to 2,3-dihydro-1H-pyrrolizine derivatives in high yields under mild conditions. PMID:27396906

  15. Thermal [4 + 2] Cycloadditions of 3-Acetyl-, 3-Carbamoyl-, and 3-Ethoxycarbonyl-Coumarins with 2,3-Dimethyl-1,3-butadiene under Solventless Conditions: A Structural Study

    Directory of Open Access Journals (Sweden)

    Itzia I. Padilla-Martínez

    2010-03-01

    Full Text Available The thermal [4+2] cycloadditions of 3-acetyl-, 3-carbamoyl, and 3-ethoxycarbonylcoumarins with 2,3-dimethyl-1,3-butadiene under solvent free conditions are reported, as well as the epoxidation reactions of some adducts. Discussion is focused on the structural features of the Diels-Alder adducts and their epoxides, based upon NMR, X-ray, and mass spectral data, and supported by ab initio theoretical calculations.

  16. N-methyl-3-pyrrolidines preparation by means of [3+2] dipoles cycloaddition reactions; Preparacion de N-metil-3-arilpirrolidinas mediante reacciones de cicloadicion dipolares [3+2

    Energy Technology Data Exchange (ETDEWEB)

    Negron, Guillermo [Universidad Autonoma Metropolitana-Azcapotzalco, Mexico, D.F. (Mexico); Fuentes, Aydee; Romero, Moises [Universidad Autonoma del Estado de Mexico, Toluca, Estado de Mexico (Mexico); Madrid, Gustavo; Cruz, Raymundo [Universidad Nacional Autonoma de Mexico, Mexico, D.F. (Mexico)

    1999-08-01

    The [3+2] cycloaddition reaction between azomethine ylide generated by deprotonation of trimethylamine N-oxide with LDA and various {alpha}-asarone derivatives to afford the corresponding pyrrolidines is described. [Spanish] Las reacciones de cicloadicion [3+2] entre iluros de azometino generados por accion del LDA sobre el N-oxido de trimetilamina y varios derivados de la {alpha}-asarona, permite la obtencion de las pirrolidinas correspondientes.

  17. Regioselective [3+2] cycloaddition of chalcones with a sugar azide: easy access to 1-(5-deoxy-D-xylofuranos-5-yl)-4,5-disubstituted-1H-1,2,3-triazoles.

    Science.gov (United States)

    Singh, Nimisha; Pandey, S K; Tripathi, Rama P

    2010-08-16

    [3+2] Cycloaddition of 5-azido-5-deoxy-1,2-O-isopropylidene-alpha-d-xylofuranose with 1,3-diphenyl-prop-3-enones, followed by oxidation of the intermediate triazolines in a tandem manner, led to the regioselective formation of 4-benzoyl-1-(5-deoxy-1,2-O-isopropylidene-alpha-d-xylofuranos-5-yl)-5-phenyl-1H-1,2,3-triazoles in moderate to good yields. PMID:20579636

  18. Rh(I)-catalyzed intramolecular [2 + 2 + 1] cycloaddition of allenenes: Construction of bicyclo[4.3.0]nonenones with an angular methyl group and tricyclo[6.4.0.01,5]dodecenone

    OpenAIRE

    Inagaki, Fuyuhiko; Itoh, Naoya; Hayashi, Yujiro; Matsui, Yumi; Mukai, Chisato

    2011-01-01

    The [RhCl(CO)dppp]2-catalyzed intramolecular carbonylative [2 + 2 + 1] cycloaddition of allenenes was developed to prepare bicyclo[4.3.0]nonenones possessing a methyl group at the ring junction, which is difficult to achieve by the Pauson–Khand reaction of the corresponding enynes. This method also provided a new procedure for the construction of the tricyclo[6.4.0.01,5]dodecenone framework in a satisfactory yield.

  19. Libraries of 2,3,4,6,7,11b-Hexahydro-1H-pyrido[2,1-a]isoquinolin-2-amine Derivatives via a Multicomponent Assembly Process/1,3-Dipolar Cycloaddition Strategy

    OpenAIRE

    Granger, Brett A.; Kaneda, Kyosuke; Martin, Stephen F.

    2011-01-01

    A Mannich-type multicomponent assembly process/1,3-dipolar cycloaddition strategy has been developed for the rapid and efficient construction of a parent tetrahydroisoquinoline fused isoxazolidine scaffold, which was subsequently functionalized using well-established protocols to access a diverse 70-membered library of novel 2,3,4,6,7,11b-hexahydro-1H-pyrido[2,1-a]isoquinoline-2-amine derivatives.

  20. Rh(I)-catalyzed intramolecular [2 + 2 + 1] cycloaddition of allenenes: Construction of bicyclo[4.3.0]nonenones with an angular methyl group and tricyclo[6.4.0.01,5]dodecenone

    OpenAIRE

    Chisato Mukai; Yumi Matsui; Yujiro Hayashi; Naoya Itoh; Fuyuhiko Inagaki

    2011-01-01

    The [RhCl(CO)dppp]2-catalyzed intramolecular carbonylative [2 + 2 + 1] cycloaddition of allenenes was developed to prepare bicyclo[4.3.0]nonenones possessing a methyl group at the ring junction, which is difficult to achieve by the Pauson–Khand reaction of the corresponding enynes. This method also provided a new procedure for the construction of the tricyclo[6.4.0.01,5]dodecenone framework in a satisfactory yield.

  1. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... with regard to longevity of total shoulders versus hips and knees. 00:46:20 GERALD WILLIAMS, MD: ... is almost ten years younger than the average hip or knee replacement patient. But if you look ...

  2. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available GLOBAL AP ANATOMIC TOTAL SHOULDER SYSTEM METHODIST HOSPITAL PHILADELPHIA, PA April 17, 2008 00:00:10 ANNOUNCER: DePuy Orthopedics is continually advancing the standard of orthopedic patient care. In a few ...

  3. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... MD: This is Doug Boardman from Richmond, Virginia. We're here at Methodist Hospital in Philadelphia, where ... will be performing a total shoulder arthroplasty. Before we go to Dr. Williams, I'd like to ...

  4. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... you look anyplace, there's probably six or eight articles in the literature right now that have compared ... Dr. Rockwood, my friend and mentor, published an article that showed pain relief was better in totals. ...

  5. Total parenteral nutrition - infants

    Science.gov (United States)

    Total parenteral nutrition (TPN) is a method of feeding that bypasses the gastrointestinal tract. Fluids are given into a vein to ... babies. It can provide a better level of nutrition than regular intravenous (IV) feedings, which provide only ...

  6. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... We had a question with regard to physical therapy after total shoulder arthroplasty: expectations and limitations. 00: ... opposite. We don't -- we do hardly any therapy at all to reverse. With reverse patients, they ...

  7. Total 2004 results

    International Nuclear Information System (INIS)

    This document presents the 2004 results of Total Group: consolidated account, special items, number of shares, market environment, adjustment for amortization of Sanofi-Aventis merger-related intangibles, 4. quarter 2004 results (operating and net incomes, cash flow), upstream (results, production, reserves, recent highlights), downstream (results, refinery throughput, recent highlights), chemicals (results, recent highlights), Total's full year 2004 results (operating and net income, cash flow), 2005 sensitivities, Total SA parent company accounts and proposed dividend, adoption of IFRS accounting, summary and outlook, main operating information by segment for the 4. quarter and full year 2004: upstream (combined liquids and gas production by region, liquids production by region, gas production by region), downstream (refined product sales by region, chemicals), Total financial statements: consolidated statement of income, consolidated balance sheet (assets, liabilities and shareholder's equity), consolidated statements of cash flows, business segments information. (J.S.)

  8. Total Ecosystem Carbon Stock

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — Total ecosystem carbon includes above- and below-ground live plant components (such as leaf, branch, stem and root), dead biomass (such as standing dead wood, down...

  9. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... And we have Dr. Song visiting us from South Korea. This patient is a 78-year-old male ... there's probably six or eight articles in the literature right now that have compared hemis to totals. ...

  10. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... be performing a total shoulder arthroplasty. Before we go to Dr. Williams, I'd like to encourage ... It's always a question about how deep we go with this osteotomy. I tend to go almost ...

  11. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available GLOBAL AP ANATOMIC TOTAL SHOULDER SYSTEM METHODIST HOSPITAL PHILADELPHIA, PA April 17, 2008 00:00:10 ANNOUNCER: DePuy Orthopedics is continually advancing the standard of orthopedic patient ...

  12. Total 2004 results

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2005-02-01

    This document presents the 2004 results of Total Group: consolidated account, special items, number of shares, market environment, adjustment for amortization of Sanofi-Aventis merger-related intangibles, 4. quarter 2004 results (operating and net incomes, cash flow), upstream (results, production, reserves, recent highlights), downstream (results, refinery throughput, recent highlights), chemicals (results, recent highlights), Total's full year 2004 results (operating and net income, cash flow), 2005 sensitivities, Total SA parent company accounts and proposed dividend, adoption of IFRS accounting, summary and outlook, main operating information by segment for the 4. quarter and full year 2004: upstream (combined liquids and gas production by region, liquids production by region, gas production by region), downstream (refined product sales by region, chemicals), Total financial statements: consolidated statement of income, consolidated balance sheet (assets, liabilities and shareholder's equity), consolidated statements of cash flows, business segments information. (J.S.)

  13. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... WILLIAMS, MD: The patients that have a total shoulder replacement will come in on their first postoperative visit and tell you their pain's gone. The hemi arthroplasty without interposition will come ...

  14. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... compared hemis to totals. Even Dr. Rockwood, my friend and mentor, published an article that showed pain ... reasonably good cortices, I get a little more aggressive, but not a lot. This is not a ...

  15. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... to longevity of total shoulders versus hips and knees. 00:46:20 GERALD WILLIAMS, MD: Well, obviously, ... ten years younger than the average hip or knee replacement patient. But if you look at the ...

  16. Total parenteral nutrition

    Science.gov (United States)

    Total parenteral nutrition (TPN) will help you or your child get nutrition from a special formula through a vein in the ... you can also eat and drink while getting nutrition from TPN. Your nurse will teach you how ...

  17. Total Grid Estimation

    OpenAIRE

    R. Kelley Pace

    1998-01-01

    This article provides a matrix representation of the adjustment grid estimator. From this representation, one can invoke the Gauss-Mrkov theorem to examine the efficiency of ordinary least squares (OLS) and the grid estimator that uses OLS estimates of the adjustments (the "plug-in" grid method). In addition, this matrix representation suggests a generalized least squares version of the grid method, labeled herin as the total grid estimator. Based on the empirical experiments, the total grid ...

  18. Total Energy Monitor

    Energy Technology Data Exchange (ETDEWEB)

    Friedrich, S

    2008-08-11

    The total energy monitor (TE) is a thermal sensor that determines the total energy of each FEL pulse based on the temperature rise induced in a silicon wafer upon absorption of the FEL. The TE provides a destructive measurement of the FEL pulse energy in real-time on a pulse-by-pulse basis. As a thermal detector, the TE is expected to suffer least from ultra-fast non-linear effects and to be easy to calibrate. It will therefore primarily be used to cross-calibrate other detectors such as the Gas Detector or the Direct Imager during LCLS commissioning. This document describes the design of the TE and summarizes the considerations and calculations that have led to it. This document summarizes the physics behind the operation of the Total Energy Monitor at LCLS and derives associated engineering specifications.

  19. Steering the azido-tetrazole equilibrium of 4-azidopyrimidines via substituent variation - implications for drug design and azide-alkyne cycloadditions.

    Science.gov (United States)

    Thomann, A; Zapp, J; Hutter, M; Empting, M; Hartmann, R W

    2015-11-21

    This paper focuses on an interesting constitutional isomerism called azido-tetrazole equilibrium which is observed in azido-substituted N-heterocycles. We present a systematic investigation of substituent effects on the isomer ratio within a 2-substituted 4-azidopyrimidine model scaffold. NMR- and IR-spectroscopy as well as X-ray crystallography were employed for thorough analysis and characterization of synthesized derivatives. On the basis of this data, we demonstrate the possibility to steer this valence tautomerism towards the isomer of choice by means of substituent variation. We show that the tetrazole form can act as an efficient disguise for the corresponding azido group masking its well known reactivity in azide-alkyne cycloadditions (ACCs). In copper(I)-catalyzed AAC reactions, substituent-stabilized tetrazoles displayed a highly decreased or even abolished reactivity whereas azides and compounds in the equilibrium were directly converted. By use of an acid sensitive derivative, we provide, to our knowledge, the first experimental basis for a possible exploitation of this dynamic isomerism as a pH-dependent azide-protecting motif for selective SPAAC conjugations in aqueous media. Finally, we demonstrate the applicability and efficiency of stabilized tetrazolo[1,5-c]pyrimidines for Fragment-Based Drug Design (FBDD) in the field of quorum sensing inhibitors. PMID:26340222

  20. Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni(II).

    Science.gov (United States)

    Das, Atanu K; Engelhard, Mark H; Lense, Sheri; Roberts, John A S; Bullock, R Morris

    2015-07-21

    Covalent tethering of P(Ph)2N(C6H4C≡CH)2 ligands (P(Ph)2N(C6H4C≡CH)2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) coupling reaction, using a BH3←P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [Ni(II)(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents Ni(II) per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, P(Ph)2N(Ph)2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [Ni(II)(diphosphine)2](2+) complex. PMID:25811536

  1. Genetically Encoded Azide Containing Amino Acid in Mammalian Cells Enables Site-Specific Antibody-Drug Conjugates Using Click Cycloaddition Chemistry.

    Science.gov (United States)

    VanBrunt, Michael P; Shanebeck, Kurt; Caldwell, Zachary; Johnson, Jeffrey; Thompson, Pamela; Martin, Thomas; Dong, Huifang; Li, Gary; Xu, Hengyu; D'Hooge, Francois; Masterson, Luke; Bariola, Pauline; Tiberghien, Arnaud; Ezeadi, Ebele; Williams, David G; Hartley, John A; Howard, Philip W; Grabstein, Kenneth H; Bowen, Michael A; Marelli, Marcello

    2015-11-18

    Antibody-drug conjugates (ADC) have emerged as potent antitumor drugs that provide increased efficacy, specificity, and tolerability over chemotherapy for the treatment of cancer. ADCs generated by targeting cysteines and lysines on the antibody have shown efficacy, but these products are heterogeneous, and instability may limit their dosing. Here, a novel technology is described that enables site-specific conjugation of toxins to antibodies using chemistry to produce homogeneous, potent, and highly stable conjugates. We have developed a cell-based mammalian expression system capable of site-specific integration of a non-natural amino acid containing an azide moiety. The azide group enables click cycloaddition chemistry that generates a stable heterocyclic triazole linkage. Antibodies to Her2/neu were expressed to contain N6-((2-azidoethoxy)carbonyl)-l-lysine at four different positions. Each site allowed over 95% conjugation efficacy with the toxins auristatin F or a pyrrolobenzodiazepine (PBD) dimer to generate ADCs with a drug to antibody ratio of >1.9. The ADCs were potent and specific in in vitro cytotoxicity assays. An anti Her2/neu conjugate demonstrated stability in vivo and a PBD containing ADC showed potent efficacy in a mouse tumor xenograph model. This technology was extended to generate fully functional ADCs with four toxins per antibody. The high stability of the azide-alkyne linkage, combined with the site-specific nature of the expression system, provides a means for the generation of ADCs with optimized pharmacokinetic, biological, and biophysical properties. PMID:26332743

  2. Host-Guest [2+2] Cycloaddition Reaction: Postsynthetic Modulation of CO2 Selectivity and Magnetic Properties in a Bimodal Metal-Organic Framework.

    Science.gov (United States)

    Hazra, Arpan; Bonakala, Satyanarayana; Bejagam, Karteek K; Balasubramanian, Sundaram; Maji, Tapas Kumar

    2016-06-01

    Simultaneous tuning of permanent porosity and modulation of magnetic properties by postsynthetic modification (PSM) with light in a metal-organic framework is unprecedented. With the aim of achieving such a photoresponsive porous magnetic material, a 3D photoresponsive biporous framework, MOF1, which has 2D channels occupied by the guest 1,2-bis(4-pyridyl)ethylene (bpee), H2 O, and EtOH molecules, has been synthesized. The guest bpee in 1 is aligned parallel to pillared bpee with a distance of 3.9 Å between the ethylenic groups; this allows photoinduced PSM of the pore surface through a [2+2] cycloaddition reaction to yield MOF2. Such photoinduced PSM of the framework structure introduces enhanced CO2 selectivity over that of N2 . The higher selectivity in MOF2 than that of MOF1 is studied through theoretical calculations. Moreover, MOF2 unveils reversible changes in Tc with response to dehydration-rehydration. This result demonstrates that photoinduced PSM is a powerful tool for fabricating novel functional materials. PMID:27113388

  3. Ionic Polymer Microspheres Bearing a Co(III) -Salen Moiety as a Bifunctional Heterogeneous Catalyst for the Efficient Cycloaddition of CO2 and Epoxides.

    Science.gov (United States)

    Leng, Yan; Lu, Dan; Zhang, Chenjun; Jiang, Pingping; Zhang, Weijie; Wang, Jun

    2016-06-01

    We report a unique strategy to obtain the bifunctional heterogeneous catalyst TBB-Bpy@Salen-Co (TBB=1,2,4,5-tetrakis(bromomethyl)benzene, Bpy=4,4'-bipyridine, Salen-Co=N,N'-bis({4-dimethylamino}salicylidene)ethylenediamino cobalt(III) acetate) by combining a cross-linked ionic polymer with a Co(III) -salen Schiff base. The catalyst showed extra high activity for CO2 fixation under mild, solvent-free reaction conditions with no requirement for a co-catalyst. The synthesized catalyst possessed distinctive spherical structural features, abundant halogen Br(-) anions with good leaving group ability, and accessible Lewis acidic Co metal centers. These unique features, together with the synergistic role of the Co and Br(-) functional sites, allowed TBB-Bpy@Salen-Co to exhibit enhanced catalytic conversion of CO2 into cyclic carbonates relative to the corresponding monofunctional analogues. This catalyst can be easily recovered and recycled five times without significant leaching of Co or loss of activity. Moreover, based on our experimental results and previous work, a synergistic cycloaddition reaction mechanism was proposed. PMID:27116117

  4. Regioselectivity in the [2 + 2] cyclo-addition reaction of triplet carbonyl compounds to substituted alkenes (Paterno-Büchi reaction): A spin-polarized conceptual DFT approach

    Indian Academy of Sciences (India)

    B Pintér; F De Proft; T Veszprémi; P Geerlings

    2005-09-01

    Regioselectivity of the photochemical [2 + 2] cyclo-addition of triplet carbonyl compounds with a series of ground state electron-rich and electron-poor alkenes, the Paterno-Büchi reaction, is studied. Activation barriers for the first step of the triplet reaction are computed in the case of the O-attack. Next, the observed regioselectivity is explained using a series of DFT-based reactivity indices. In the first step, we use the local softness and the local HSAB principle within a softness matching approach, and explain the relative activation barriers of the addition step. In the final step, the regioselectivity is assessed within the framework of spin-polarized conceptual density functional theory, considering response functions of the system's external potential , number of electrons and spin number , being the difference between the number of and electrons in the spin-polarized system. Although the concept of local spin philicity, introduced recently within this theory, appears less suited to predict the regioselectivity in this reaction, the correct regioselectivity emerges from considering an interaction between the largest values of the generalized Fukui functions ss on both interacting molecules.

  5. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... AP ANATOMIC TOTAL SHOULDER SYSTEM METHODIST HOSPITAL PHILADELPHIA, PA April 17, 2008 00:00:10 ANNOUNCER: DePuy ... you don't make a bunch of small passes at the lesser tuberosity and make it a ...

  6. Total Synthesis of (-)-Cardiopetaline.

    Science.gov (United States)

    Nishiyama, Yoshitake; Yokoshima, Satoshi; Fukuyama, Tohru

    2016-05-20

    The total synthesis of (-)-cardiopetaline, an aconitine-type natural product, has been accomplished. Our synthesis involved a Wagner-Meerwein rearrangement of a sulfonyloxirane that enabled, in a single step, the construction of the bicyclo[3.2.1] system in the aconitine skeleton and effective introduction of oxygen functional groups at the appropriate positions. PMID:27166640

  7. Supravaginal eller total hysterektomi?

    DEFF Research Database (Denmark)

    Edvardsen, L; Madsen, E M

    1994-01-01

    There has been a decline in the rate of hysterectomies in Denmark in general over the last thirteen years, together with a rise in the number of supravaginal operations over the last two years. The literature concerning the relative merits of the supravaginal and the total abdominal operation is ...... indicate a reduced frequency of orgasm after the total hysterectomy compared with the supravaginal operation. When there are technical problems peroperatively with an increased urologic risk the supravaginal operation is recommended....... examined. It is concluded that the risk of developing carcinoma of the cervical stump is low, and no longer a weighty indication for the total in preference to the supravaginal hysterectomy as long as subsequent screening of the cervix is performed. At the same time it is important to inform the women......There has been a decline in the rate of hysterectomies in Denmark in general over the last thirteen years, together with a rise in the number of supravaginal operations over the last two years. The literature concerning the relative merits of the supravaginal and the total abdominal operation is...

  8. Total Cost of Ownership

    DEFF Research Database (Denmark)

    Zachariassen, Frederik

    2007-01-01

    Total Cost of Ownership (TCO), som giver et bud på, hvordan virksomheder kan opnå en bedre indsigt i, hvilke leverandører der forårsager hvilke omkostninger og dermed danne et forbedret beslutningsgrundlag for besparelser i leverandørleddet. I artiklen argumenteres først og fremmest for, hvorfor TCO er...

  9. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... to longevity of total shoulders versus hips and knees. 00:46:20 GERALD WILLIAMS, MD: Well, obviously, if you look at -- it depends upon who you put them in. First of all, the young-- the youngest patient population for joint replacement in the United States by far, by ...

  10. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... Anatomic Total Shoulder surgery, which featured the latest innovation in shoulder surgery from DePuy Orthopedics. OR-Live makes it easy for you to learn more. Just click on the "Request Information" button on your webcast screen and open the door to informed medical care. 01:21: ...

  11. "Total Deposition (TDEP) Maps"

    Science.gov (United States)

    The presentation provides an update on the use of a hybrid methodology that relies on measured values from national monitoring networks and modeled values from CMAQ to produce of maps of total deposition for use in critical loads and other ecological assessments. Additionally, c...

  12. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... put totals in unless they're under the age of 50. But as the patient gets older, ... I'll give you an example: 26-year-old juvenile rheumatoid arthritic. You can pulse-irrigate that, ...

  13. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... advancing the standard of orthopedic patient care. In a few moments, you'll be able to watch a live global AP anatomic total shoulder surgery from Methodist Hospital in Philadelphia. A revolution in shoulder orthopedics, the Global AP gives ...

  14. Total versus subtotal hysterectomy

    DEFF Research Database (Denmark)

    Gimbel, Helga; Zobbe, Vibeke; Andersen, Anna Birthe; Gluud, Christian; Ottesen, Bent S; Tabor, Ann

    2005-01-01

    The aim of this study was to compare total and subtotal abdominal hysterectomy for benign indications, with regard to urinary incontinence, postoperative complications, quality of life (SF-36), constipation, prolapse, satisfaction with sexual life, and pelvic pain at 1-year postoperative. Eighty...

  15. Anatomic Total Shoulder System

    Medline Plus

    Full Text Available ... by almost ten years, is shoulders. So by definition, the average shoulder-replacement patient is almost ten ... Anatomic Total Shoulder surgery, which featured the latest innovation in shoulder surgery from DePuy Orthopedics. OR-Live ...

  16. Total Cross Sections

    OpenAIRE

    G. GiacomelliBologna University and INFN

    2014-01-01

    The measurements of the hadron-hadron total cross sections are the first measurements performed when a new hadron accelerator opens up a new energy region; the measurements were made as function of the incoming beam momentum or c.m. energy and have often been repeated with improved accuracy and finer energy spacing.

  17. CSF total protein

    Science.gov (United States)

    CSF total protein is a test to determine the amount of protein in your spinal fluid, also called cerebrospinal fluid (CSF). ... The normal protein range varies from lab to lab, but is typically about 15 to 60 mg/dL. Note: mg/dL = ...

  18. Total 2004 annual report

    International Nuclear Information System (INIS)

    This annual report of the Group Total brings information and economic data on the following topics, for the year 2004: the corporate governance, the corporate social responsibility, the shareholder notebook, the management report, the activities, the upstream (exploration and production) and downstream (refining and marketing) operating, chemicals and other matters. (A.L.B.)

  19. Total Quality Management Seminar.

    Science.gov (United States)

    Massachusetts Career Development Inst., Springfield.

    This booklet is one of six texts from a workplace literacy curriculum designed to assist learners in facing the increased demands of the workplace. The booklet contains seven sections that cover the following topics: (1) meaning of total quality management (TQM); (2) the customer; (3) the organization's culture; (4) comparison of management…

  20. Total Quality Management Simplified.

    Science.gov (United States)

    Arias, Pam

    1995-01-01

    Maintains that Total Quality Management (TQM) is one method that helps to monitor and improve the quality of child care. Lists four steps for a child-care center to design and implement its own TQM program. Suggests that quality assurance in child-care settings is an ongoing process, and that TQM programs help in providing consistent, high-quality…

  1. Total 2003 Results

    International Nuclear Information System (INIS)

    This document presents the 2003 results of Total Group: consolidated account, special items, number of shares, market environment, 4. quarter 2003 results, full year 2003 results, upstream (key figures, proved reserves), downstream key figures, chemicals key figures, parent company accounts and proposed dividends, 2004 sensitivities, summary and outlook, operating information by segment for the 4. quarter and full year 2003: upstream (combined liquids and gas production by region, liquids production by region, gas production by region), downstream (refinery throughput by region, refined product sales by region, chemicals), impact of allocating contribution of Cepsa to net operating income by business segment: equity in income (loss) and affiliates and other items, Total financial statements: consolidated statement of income, consolidated balance sheet (assets, liabilities and shareholder's equity), consolidated statements of cash flows, business segments information. (J.S.)

  2. Total - annual report 2005

    International Nuclear Information System (INIS)

    This annual report presents the activities and results of TOTAL S.A., french society on oil and gas. It deals with statistics, the managers, key information on financial data and risk factors, information on the Company, unresolved Staff Comments, employees, major Shareholders, consolidated statements, markets, security, financial risks, defaults dividend arrearages and delinquencies, controls and procedures, code of ethics and financial statements. (A.L.B.)

  3. Total Synthesis of Millingtonine.

    Science.gov (United States)

    Brown, Patrick D; Lawrence, Andrew L

    2016-07-11

    Millingtonine is a glycosidic alkaloid that exists as a pair of pseudo-enantiomeric diastereomers. Consideration of the likely biosynthetic origins of this unusual natural product has resulted in the development of a seven-step total synthesis. Results from this synthetic work provide evidence in support of a proposed network of biosynthetic pathways that can account for the formation of several phenylethanoid natural products. PMID:27249628

  4. Total synthesis of teixobactin.

    Science.gov (United States)

    Jin, Kang; Sam, Iek Hou; Po, Kathy Hiu Laam; Lin, Du'an; Ghazvini Zadeh, Ebrahim H; Chen, Sheng; Yuan, Yu; Li, Xuechen

    2016-01-01

    To cope with the global bacterial multidrug resistance, scientific communities have devoted significant efforts to develop novel antibiotics, particularly those with new modes of actions. Teixobactin, recently isolated from uncultured bacteria, is considered as a promising first-in-class drug candidate for clinical development. Herein, we report its total synthesis by a highly convergent Ser ligation approach and this strategy allows us to prepare several analogues of the natural product. PMID:27484680

  5. Total synthesis of ochnaflavone

    OpenAIRE

    Monica M. Ndoile; van Heerden, Fanie R

    2013-01-01

    The first total syntheses of ochnaflavone, an asymmetric biflavone consisting of apigenin and luteolin moieties, and the permethyl ether of 2,3,2'',3''-tetrahydroochnaflavone have been achieved. The key steps in the synthesis of ochnaflavone were the formation of a diaryl ether and ring cyclization of an ether-linked dimeric chalcone to assemble the two flavone nuclei. Optimal experimental conditions for the oxidative cyclization to form ochnaflavone were established.

  6. Total synthesis of ochnaflavone

    Directory of Open Access Journals (Sweden)

    Monica M. Ndoile

    2013-07-01

    Full Text Available The first total syntheses of ochnaflavone, an asymmetric biflavone consisting of apigenin and luteolin moieties, and the permethyl ether of 2,3,2'',3''-tetrahydroochnaflavone have been achieved. The key steps in the synthesis of ochnaflavone were the formation of a diaryl ether and ring cyclization of an ether-linked dimeric chalcone to assemble the two flavone nuclei. Optimal experimental conditions for the oxidative cyclization to form ochnaflavone were established.

  7. Boosting Total Relationship Marketing

    OpenAIRE

    Aykut, Arslan

    2008-01-01

    This paper explores the track of marketing, by referring to the literature, through the advancements in digitalized technological systems particularly Information Technologies (IT), the emergence of a more broadly educated and more discerning consumer with increasing discretionary spending and purchasing power, the adoption of Total Quality Management (TQM) as the biggest competitive issue of 1990s, the growth of the service economy, the increase of competitive intensity and its impact on cus...

  8. Total Logistic Plant Solutions

    Directory of Open Access Journals (Sweden)

    Dusan Dorcak

    2016-02-01

    Full Text Available The Total Logistics Plant Solutions, plant logistics system - TLPS, based on the philosophy of advanced control processes enables complex coordination of business processes and flows and the management and scheduling of production in the appropriate production plans and planning periods. Main attributes of TLPS is to create a comprehensive, multi-level, enterprise logistics information system, with a certain degree of intelligence, which accepts the latest science and research results in the field of production technology and logistics. Logistic model of company understands as a system of mutually transforming flows of materials, energy, information, finance, which is realized by chain activities and operations

  9. Total Synthesis of Teixobactin.

    Science.gov (United States)

    Giltrap, Andrew M; Dowman, Luke J; Nagalingam, Gayathri; Ochoa, Jessica L; Linington, Roger G; Britton, Warwick J; Payne, Richard J

    2016-06-01

    The first total synthesis of the cyclic depsipeptide natural product teixobactin is described. Synthesis was achieved by solid-phase peptide synthesis, incorporating the unusual l-allo-enduracididine as a suitably protected synthetic cassette and employing a key on-resin esterification and solution-phase macrolactamization. The synthetic natural product was shown to possess potent antibacterial activity against a range of Gram-positive pathogenic bacteria, including a virulent strain of Mycobacterium tuberculosis and methicillin-resistant Staphylococcus aureus (MRSA). PMID:27191730

  10. Total quality accounting

    Directory of Open Access Journals (Sweden)

    Andrijašević Maja

    2008-01-01

    Full Text Available The focus of competitive "battle" shifted from the price towards non-price instruments, above all, towards quality that became the key variable for profitability increase and achievement of better comparative position of a company. Under such conditions, management of a company, which, according to the established and certified system of total quality, strives towards achieving of a better market position, faces the problem of quality cost measurement and determination. Management, above all, cost accounting can help in solving of this problem, but the question is how much of its potential is being used for that purpose.

  11. TOTAL annual report 2003

    International Nuclear Information System (INIS)

    This 2003 annual report of the Group Total provides economical results and information of the society on the following topics: keys data, the corporate governance (Directors charter, board of directors, audit committee, nomination and remuneration committee, internal control procedures, compensation of directors and executive officers), the corporate social responsibility (environmental stewardship, the future of energy management, the safety enhancement, the human resources, ethics and local development), the investor relations, the management report, the upstream exploration and production, the downstream refining, marketing, trading and shipping, the chemicals and financial and legal information. (A.L.B.)

  12. Total Factbook 2003

    International Nuclear Information System (INIS)

    This report presents the activities and results of the Group Total-Fina-Elf for the year 2003. It brings information and economic data on the following topics: the corporate and business; the upstream activities with the reserves, the costs, standardized measure and changes of discounted future net cash flow,oil and gas acreage, drilling, liquefied natural gas, pipelines; downstream activities with refining and marketing maps, refinery, petroleum products, sales, retail gasoline outlets; chemicals with sales and operating income by sector, major applications, base chemicals and polymers, intermediates and performance polymers. (A.L.B.)

  13. Total 2004 fact book

    International Nuclear Information System (INIS)

    This report presents the activities and results of the Group Total-Fina-Elf for the year 2004. It brings information and economic data on the following topics: the corporate and business; the upstream activities with the reserves, the costs, standardized measure and changes of discounted future net cash flow,oil and gas acreage, drilling, liquefied natural gas, pipelines; downstream activities with refining and marketing maps, refinery, petroleum products, sales, retail gasoline outlets; chemicals with sales and operating income by sector, major applications, base chemicals and polymers, intermediates and performance polymers. (A.L.B.)

  14. Total quality is people

    International Nuclear Information System (INIS)

    Confronted by changing market conditions and increased global competition, in 1983 the Commercial Nuclear Fuel Division (CNFD) of Westinghouse Electric embarked on an ambitious plan to make total quality the centerpiece of its long-term business strategy. Five years later, the division's efforts in making continuous quality improvement a way of life among its more than 2,000 employees gained national recognition when it was named a charter recipient of the Malcolm Baldridge National Quality Award. What CNFD achieved during the 1980s was a cultural transformation, characterized by an empowered work force committed to a common vision. The company's quality program development strategy is described

  15. Immediate total tooth replacement.

    Science.gov (United States)

    Garber, D A; Salama, M A; Salama, H

    2001-03-01

    Successful implant placement at the time of extraction has been documented. Implant placement at the time of extraction was initially performed as a two-stage procedure often with barrier membranes and sophisticated second-stage surgical uncoverings. The authors describe the next generation of this technique, including atraumatic tooth removal with simultaneous root form, implant placement, and temporization at one appointment. This technique of "Immediate Total Tooth Replacement" allows for the maintenance of the bony housing and soft-tissue form that existed before extraction, while at the same time establishing a root form anchor in the bone for an esthetic restoration. PMID:11913258

  16. Site-specific bioconjugation of a murine dihydrofolate reductase enzyme by copper(I-catalyzed azide-alkyne cycloaddition with retained activity.

    Directory of Open Access Journals (Sweden)

    Sung In Lim

    Full Text Available Cu(I-catalyzed azide-alkyne cycloaddition (CuAAC is an efficient reaction linking an azido and an alkynyl group in the presence of copper catalyst. Incorporation of a non-natural amino acid (NAA containing either an azido or an alkynyl group into a protein allows site-specific bioconjugation in mild conditions via CuAAC. Despite its great potential, bioconjugation of an enzyme has been hampered by several issues including low yield, poor solubility of a ligand, and protein structural/functional perturbation by CuAAC components. In the present study, we incorporated an alkyne-bearing NAA into an enzyme, murine dihydrofolate reductase (mDHFR, in high cell density cultivation of Escherichia coli, and performed CuAAC conjugation with fluorescent azide dyes to evaluate enzyme compatibility of various CuAAC conditions comprising combination of commercially available Cu(I-chelating ligands and reductants. The condensed culture improves the protein yield 19-fold based on the same amount of non-natural amino acid, and the enzyme incubation under the optimized reaction condition did not lead to any activity loss but allowed a fast and high-yield bioconjugation. Using the established conditions, a biotin-azide spacer was efficiently conjugated to mDHFR with retained activity leading to the site-specific immobilization of the biotin-conjugated mDHFR on a streptavidin-coated plate. These results demonstrate that the combination of reactive non-natural amino acid incorporation and the optimized CuAAC can be used to bioconjugate enzymes with retained enzymatic activity.

  17. Total organic carbon analyzer

    Science.gov (United States)

    Godec, Richard G.; Kosenka, Paul P.; Smith, Brian D.; Hutte, Richard S.; Webb, Johanna V.; Sauer, Richard L.

    1991-01-01

    The development and testing of a breadboard version of a highly sensitive total-organic-carbon (TOC) analyzer are reported. Attention is given to the system components including the CO2 sensor, oxidation reactor, acidification module, and the sample-inlet system. Research is reported for an experimental reagentless oxidation reactor, and good results are reported for linearity, sensitivity, and selectivity in the CO2 sensor. The TOC analyzer is developed with gravity-independent components and is designed for minimal additions of chemical reagents. The reagentless oxidation reactor is based on electrolysis and UV photolysis and is shown to be potentially useful. The stability of the breadboard instrument is shown to be good on a day-to-day basis, and the analyzer is capable of 5 sample analyses per day for a period of about 80 days. The instrument can provide accurate TOC and TIC measurements over a concentration range of 20 ppb to 50 ppm C.

  18. Total ankle joint replacement.

    Science.gov (United States)

    2016-02-01

    Ankle arthritis results in a stiff and painful ankle and can be a major cause of disability. For people with end-stage ankle arthritis, arthrodesis (ankle fusion) is effective at reducing pain in the shorter term, but results in a fixed joint, and over time the loss of mobility places stress on other joints in the foot that may lead to arthritis, pain and dysfunction. Another option is to perform a total ankle joint replacement, with the aim of giving the patient a mobile and pain-free ankle. In this article we review the efficacy of this procedure, including how it compares to ankle arthrodesis, and consider the indications and complications. PMID:26868932

  19. Total quality at source

    International Nuclear Information System (INIS)

    The Total Quality at Source philosophy is based on optimizing the effectiveness of people in achieving ZERO-DEFECT results. In this paper a philosophy of what, I have come to perceive, it takes to get people to perform to the very best of their abilities and thereby achieve the best results they can, is presented. In the examples I shall describe I have played an instrumental role since it has become my belief that any job can always be done better provided that the people doing it can themselves become convinced that they can do better. Clearly there are many ideas on how to do this. The philosophy that I am presenting in this paper is based on my own experience, where I have both participated and observed it being applied; its effectiveness may be judged by the results. (author)

  20. Total Integrative Evolutionary Communication

    DEFF Research Database (Denmark)

    Nedergaard Thomsen, Ole; Brier, Søren

    2014-01-01

    and, on the other, Peircean biosemiotics. According to Cybersemiotics, language is primarily a creative process of total integrative evolutionary communication. It comprises three evolutionary stages: (1) biological reflexive languaging (the reflexive foundation of social coordination), (2......). In this inclusive hierarchy language games subsume the other stages, and thus human evolutionary communication is primarily a symbolic-conventional practice. It is intertwined with the practice of living, that is, with different life forms, including other forms of semiotic behavior. Together they form a coherent...... biological and socio-cultural practice. The basic “molecule” of the cybersemiotic model of human communication is a dyad between two linguistic cyborgs, alias natural language users. Single human communicators are thus “atoms”. They are hybrids between nature and nurture, manipulating all sorts...

  1. Intermolecular cycloaddition of nonstabilized azomethine ylides generated from 1,3-thiazolidine-4-carboxylic acids: synthesis of 5,7a-dihydro-1H,3H-pyrrolo[1,2-c]thiazoles

    OpenAIRE

    Cardoso, Ana L.; Kaczor, Agnieszka; Silva, Artur M. S.; Fausto, Rui; Melo, Teresa M.V.D. Pinho e; Gonsalves, António M. D'A Rocha

    2006-01-01

    The 1,3-dipolar cycloaddition of dimethyl acetylenedicarboxylate with nonstabilized azomethine ylides, generated via the decarboxylative condensation of 1,3-thiazolidine-4-carboxylic acids with aldehydes, afforded 5,7a-dihydro-1H,3H-pyrrolo[1,2-c]thiazole derivatives. 2-Substituted-1,3-thiazolidine-4-carboxylic acids led to the stereoselective formation of 5,7a-dihydro-1H,3H-pyrrolo[1,2-c]thiazoles. Quantum-chemistry calculations were carried out allowing the rationalization of the observed s...

  2. L-Proline catalyzed one-step synthesis of 4,5-diaryl-2H-1,2,3-triazoles from heteroaryl cyanostilbenes via [3+2] cycloaddition of azide

    OpenAIRE

    Penthala, Narsimha Reddy; Madadi, Nikhil Reddy; Janganati, Venumadhav; Crooks, Peter A.

    2014-01-01

    Use of a novel reagent has been established for the synthesis of a series of 4,5-diaryl-2H-1,2,3-triazoles (6a-i and 9a-e) from cyanostilbene analogs of benzo[b]thiophene, benzo[b]furan and indole, catalyzed by L-proline via Lewis base-catalyzed one-step [3+2]cycloaddition of azide. This method provides an efficient, simple and environmentally benign procedure that affords good yields and relatively short reaction times.

  3. Diels-alder cycloaddition of 2-azadienes to methyl 2-(2,6-dichlorophenyl)-2H-azirine-3-carboxylate in the synthesis of methyl 4-oxo-1,3-diazabicyclo[4.1.0]heptane-6-carboxylates

    OpenAIRE

    Alves, M. José; Durães, M. Miguel; Fortes, A. Gil

    2004-01-01

    A number of fused 4-oxo-1,3-diazabicyclo[4.1.0]heptane-6-carboxylates, a new type of compound, have been obtained by Diels-Alder cycloaddition between nucleophilic 2-azadienes and an electrophilic 2H-azirine. The reactions are completely endo- and regioselective, the azirine being added by its less hindered face to the diene. There are two isomers 7 and 8 formed from dienes 1 due either to isomerization of the cycloadducts 7 and 8 or by isomerization of the C=N bond of the diene during the re...

  4. Organometallic Enantiomeric Scaffolding: General Access to 2-Substituted Oxa- and Azabicyclo[3.2.1]octenes via a Brønsted Acid-catalyzed [5+2] Cycloaddition Reaction

    OpenAIRE

    Garnier, Ethel C.; Liebeskind, Lanny S.

    2008-01-01

    6-Substituted TpMo(CO)2(η-2,3,4-pyranyl)- and TpMo(CO)2(η-2,3,4-pyridinyl) scaffolds (Tp = hydridotrispyrazolylborato) function as reaction partners in an efficient regio- and stereocontrolled synthesis of functionalized oxa- and azabicyclo[3.2.1]octenes through a novel Brønsted acid-catalyzed [5+2] cycloaddition reaction. Excellent exo-selectivities are obtained and the reaction gives products with complete retention of enantiomeric purity when carried out with chiral, non-racemic scaffolds....

  5. Total disc replacement.

    Science.gov (United States)

    Vital, J-M; Boissière, L

    2014-02-01

    Total disc replacement (TDR) (partial disc replacement will not be described) has been used in the lumbar spine since the 1980s, and more recently in the cervical spine. Although the biomechanical concepts are the same and both are inserted through an anterior approach, lumbar TDR is conventionally indicated for chronic low back pain, whereas cervical TDR is used for soft discal hernia resulting in cervicobrachial neuralgia. The insertion technique must be rigorous, with precise centering in the disc space, taking account of vascular anatomy, which is more complex in the lumbar region, particularly proximally to L5-S1. All of the numerous studies, including prospective randomized comparative trials, have demonstrated non-inferiority to fusion, or even short-term superiority regarding speed of improvement. The main implant-related complication is bridging heterotopic ossification with resulting loss of range of motion and increased rates of adjacent segment degeneration, although with an incidence lower than after arthrodesis. A sufficiently long follow-up, which has not yet been reached, will be necessary to establish definitively an advantage for TDR, particularly in the cervical spine. PMID:24412045

  6. Total process surveillance (TOPS)

    International Nuclear Information System (INIS)

    Understanding the current operating behaviour of a process or power plant is the key to maximizing the efficiency and safety of operation and the quality of the product. Early detection of plant component or sensor degradation and failure improves operating safety, product quality and plant availability. This paper describes the design and development of a Total Process Surveillance system which assimilates all the sensor information available on a plant to provide the operators with a succinct report on the status of the plant behaviour. The heart of the system is a robust model-based observer which can estimate internal plant states, and provides a residual signal with powerful fault detection and isolation features. Several results are presented which illustrate the performance of the system in detecting and isolating multiple fault scenarios in a fast reactor plant. A structure for the practical implementation of the system is described, and comments are given on its contribution to the final experimental work planned for AEA Technology's Prototype Fast Reactor (PFR). (Author)

  7. Total quality management

    OpenAIRE

    Цветкова, Наталья

    1993-01-01

    В статье рассматриваются пути улучшения качества образования вообще и лингвистического образования в частности посредством использования системы качества Total Quality Management. Охарактеризованы ее четыре этапа - планирование, управление, обеспечение и улучшение. Анализируются основные направления использования системы качества в обучении иностранному языку....

  8. Total Process Surveillance (TOPS)

    International Nuclear Information System (INIS)

    analytical redundancy is of significant importance in order to obtain the maximum amount of information as to the state of the plant. A further logical step in this theory is the accommodation of failed or damaged transducers by deriving their measurement information from the available remaining transducers. A system capable of providing a clear and improved picture of the plant's behaviour under a range of normal and off-normal operating conditions would thus be of significant economical and safety benefit. In summary: A Total Process Surveillance system is under development which can provide, in real-time, additional process information from a limited number of raw measurement signals. This is achieved by using a robust model based observer to generate estimates of the process' internal states. The observer utilises the analytical redundancy among a diverse range of transducers and can thus accommodate off-normal conditions which lead to transducer loss or damage. The modular hierarchical structure of the system enables the maximum amount of information to be assimilated from the available instrument signals no matter how diverse. This structure also constitutes a data reduction path thus reducing operator cognitive overload from a large number of varying, and possibly contradictory, raw plant signals. The TOPS system provides a structured and complete means for plant data management under both normal and off-normal operating conditions and thus will significantly assist the operator during severe accident management

  9. Regio- and Stereoselective 1,3-Dipolar Cycloaddition of Cyclic Azomethine Imines to Platinum(IV)-Bound Nitriles Giving Δ(2)-1,2,4-Triazoline Species.

    Science.gov (United States)

    Smirnov, Andrey S; Kritchenkov, Andreii S; Bokach, Nadezhda A; Kuznetsov, Maxim L; Selivanov, Stanislav I; Gurzhiy, Vladislav V; Roodt, Andreas; Kukushkin, Vadim Yu

    2015-11-16

    The complex trans-[PtCl4(EtCN)2] (14) reacts smoothly at 25 °C with the stable cyclic azomethine imines R(1)CH═N(a)NC(O)CH(NHC(O)C6H4R(3))C(b)H(C6H4R(2))((a-b)) [R(1)/R(2)/R(3) = p-Me/H/H (8); p-Me/p-Me/H (9); p-Me/p-MeO/H (10); p-Me/p-Cl/p-Cl (11); p-MeO/p-Me/H (12); p-MeO/p-Cl/m-Me (13)], and the reaction proceeds as stereoselective 1,3-dipolar cycloaddition to one of the EtCN ligands accomplishing the monocycloadducts trans-[PtCl4(EtCN){N(a)═C(Et)N(b)C(O)CH(NHC(O)C6H4R(3))CH(C6H4R(2))N(c)C(d)HR(1)}])((a-d;b-c)) [R(1)/R(2)/R(3) = p-Me/H/H (15); p-Me/p-Me/H (16); p-Me/p-MeO/H (17); p-Me/p-Cl/p-Cl (18); p-MeO/p-Me/H (19); p-MeO/p-Cl/m-Me (20)]. Inspection of the obtained and literature data indicate that the cycloaddition of the azomethine imines to the C≡N bonds of HCN and of Pt(IV)-bound EtCN has different regioselectivity leading to Δ(2)-1,2,3-triazolines and Δ(2)-1,2,4-triazolines, respectively. Platinum(II) species trans-[PtCl2(EtCN){N(a)═C(Et)N(b)C(O)CH(NHC(O)C6H4R(3))CH(C6H4R(2))N(c)C(d)HR(1)}]((a-d;b-c)) [R(1)/R(2)/R(3) = p-Me/H/H (21); p-Me/p-Me/H (22); p-Me/p-MeO/H (23); p-Me/p-Cl/p-Cl (24); p-MeO/p-Me/H (25); p-MeO/p-Cl/m-Me (26)] were obtained by a one-pot procedure from 14 and 8-13 followed by addition of the phosphorus ylide Ph3P═CHCO2Me. Δ(2)-1,2,4-Triazolines N(a)═C(Et)N(b)C(O)CH(NHC(O)C6H4R(3))CH(C6H4R(2))N(c)C(d)HR(1(a-d;b-c)) [R(1)/R(2)/R(3) = p-Me/H/H (27); p-Me/p-Me/H (28); p-Me/p-MeO/H (29); p-Me/p-Cl/p-Cl (30); p-MeO/p-Me/H (31); p-MeO/p-Cl/m-Me (32)] were liberated from 21-26 by the treatment with bis(diphenylphosphyno)ethane (dppe). Platinum(II) complexes 21-26 were characterized by elemental analyses (C, H, N), high-resolution electrospray ionization mass spectrometry (ESI-MS), and IR and (1)H and (13)C{(1)H} NMR spectroscopies and single crystal X-ray diffraction in the solid state for 25·CH3OH, 26·(CHCl3)0.84. The structure of 26 was also determined by COSY-90 and NOESY NMR methods in solution. Quantitative evaluation

  10. Total Knee Replacement for Women

    Medline Plus

    Full Text Available ... ll be moderating a Zimmer Gender Solutions total knee, performed by my partner, Dr. Ken Gustke. At ... I’m going to be doing a total knee replacement utilizing the Gender Flex implants on a ...

  11. Green synthesis of copper nanoparticles using Ginkgo biloba L. leaf extract and their catalytic activity for the Huisgen [3+2] cycloaddition of azides and alkynes at room temperature.

    Science.gov (United States)

    Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad

    2015-11-01

    During this study, we report the green synthesis of copper nanoparticles (Cu NPs) using Ginkgo biloba L. leaf extract as a reducing and stabilizing agent under surfactant-free conditions. The formation of Cu NPs is monitored by recording the UV-vis absorption spectra. The green synthesized Cu NPs are characterized by TEM, EDS, FT-IR and UV-visible techniques. According to UV-vis results, the synthesized Cu NPs by this method are quite stable even after one month indicating the stability of Cu NPs. In terms of environmental impact and economy, metallic Cu NPs offer several advantages over homogeneous and traditional heterogeneous catalysts. In addition, due to the increased metal surface area, Cu NPs shows very high catalytic activity for the Huisgen [3+2] cycloaddition of azides and alkynes at room temperature. Furthermore, the catalyst can be simply recovered and reused several times with almost no loss in activity. PMID:26164245

  12. Regio- and stereoselective synthesis of pregnane-fused isoxazolines by nitril-oxide/alkene 1,3-dipolar cycloaddition and an evaluation of their cell-growth inhibitory effect in vitro

    Science.gov (United States)

    Mótyán, Gergő; Baji, Ádám; Zupkó, István; Frank, Éva

    2016-04-01

    Efficient syntheses of some pregnane-fused isoxazolines from 16-dehydropregnenolone acetate with different arylnitrile oxides were carried out by 1,3-dipolar cycloadditions. The intermolecular ring-closures occurred in a highly regio- and stereoselective manner permitting the formation of a single 16α,17α-condensed diastereomer in which the O terminus of the nitrile oxide dipole is attached to C-17 of the sterane core. The conversions were found to be affected significantly by the electronic character of the substituents on the aromatic moiety of the 1,3-dipoles. Deacetylation of the primary products resulted in the corresponding 3β-OH analogs. All of the synthesized compounds were subjected to in vitro pharmacological studies for the determination of their antiproliferative effects on four breast cancer cell lines (MCF7, T47D, MDA-MB-231 and MDA-MB-361).

  13. Regular Totally Separable Sphere Packings

    OpenAIRE

    Reid, Samuel

    2015-01-01

    The topic of totally separable sphere packings is surveyed with a focus on regular constructions, uniform tilings, and contact number problems. An enumeration of all regular totally separable sphere packings in $\\mathbb{R}^2$, $\\mathbb{R}^3$, and $\\mathbb{R}^4$ which are based on convex uniform tessellations, honeycombs, and tetracombs, respectively, is presented, as well as a construction of a family of regular totally separable sphere packings in $\\mathbb{R}^d$ that is not based on a convex...

  14. Signed Total Domination in Graphs

    Institute of Scientific and Technical Information of China (English)

    邢化明; 孙良; 陈学刚

    2003-01-01

    Let G=(V,E) be a simple graph. For any real valued function f:V→R, the weight of f is f(V)=∑f(v) over all vertices v∈V. A signed total dominating function is a function f:V→{-1,1} such that f(N(v))≥1 for every vertex v∈V. The signed total domination number of a graph G equals the minimum weight of a signed total dominating function on G. In this paper, some properties of the signed total domination number of a graph G are discussed.

  15. Total syntheses of the telomerase inhibitors dictyodendrin B, C, and E.

    Science.gov (United States)

    Fürstner, Alois; Domostoj, Mathias M; Scheiper, Bodo

    2006-06-21

    Concise and flexible total syntheses of the pyrrolo[2,3-c]carbazole alkaloids dictyodendrin B (2), C (3), and E (5) are described. These polycyclic telomerase inhibitors of marine origin derive from the common intermediate 18 which was prepared on a multigram scale by a sequence comprising a TosMIC cycloaddition with formation of the pyrrole A-ring, a titanium-induced reductive oxoamide coupling reaction to generate an adjacent indole nucleus, and a photochemical 6pi-electrocyclization/aromatization tandem to forge the pyrrolocarbazole core. Conversion of 18 into dictyodendrin C required selective manipulations of the lateral protecting groups and oxidation with peroxoimidic acid to form the vinylogous benzoquinone core of the target. Zinc-induced reductive cleavage of the trichloroethyl sulfate ester then completed the first total synthesis of 3. Its relatives 2 and 5 also originate from compound 18 by a selective bromination of the pyrrole entity followed by elaboration of the resulting bromide 27 via metal-halogen exchange or cross-coupling chemistry, respectively. Particularly noteworthy in this context is the generation of the very labile p-quinomethide motif of dictyodendrin E by a palladium-catalyzed benzyl cross-coupling reaction followed by vinylogous oxidation of the resulting product 41 with DDQ. The Suzuki step could only be achieved with the aid of the borate complex 40 formed in situ from p-methoxybenzylmagnesium chloride and 9-MeO-9-BBN, whereas alternative methods employing benzylic boronates, -trifluoroborates, or -stannanes met with failure. PMID:16771525

  16. Cogema acquires TOTAL's uranium assets

    International Nuclear Information System (INIS)

    On April 28, France's nuclear fuel cycle conglomerate Cogema and petroleum group TOTAL announced a plan in which Cogema will assume ownership of TOTAL's uranium assets worldwide, and as part of the deal, each firm will acquire shares of the other. On June 2, the agreement will be submitted to shareholders and, assuming it is approved, will go into effect this year. The agreement calls for TOTAL to acquire a 10.8-percent share in Cogema, thus becoming its first private sector shareholder, by underwriting a reserve capital increase of FF1.5 billion (approximately US$283 million). In return, Cogema will pay FF2.52 billion for approximately 4.3 percent of TOTAL, as part of a reserve capital increase totalling FF4.07 billion

  17. Totality eclipses of the Sun

    CERN Document Server

    Littmann, Mark; Willcox, Ken

    2008-01-01

    A total eclipse of the Sun is the most awesome sight in the heavens. Totality: Eclipses of the Sun takes you to eclipses of the past, present, and future, and lets you see - and feel - why people travel to the ends of the Earth to observe them. - ;A total eclipse of the Sun is the most awesome sight in the heavens. Totality: Eclipses of the Sun takes you to eclipses of the past, present, and future, and lets you see - and feel - why people travel to the ends of the Earth to observe them. Totality: Eclipses of the Sun is the best guide and reference book on solar eclipses ever written. It explains: how to observe them; how to photograph and videotape them; why they occur; their history and mythology; and future eclipses - when and where to see them. Totality also tells the remarkable story of how eclipses shocked scientists, revealed the workings of the Sun, and made Einstein famous. And the book shares the experiences and advice of many veteran eclipse observers. Totality: Eclipses of the Sun is profusely ill...

  18. The first Polish total laryngectomies

    OpenAIRE

    Kierzek, Andrzej; Paprocka-Borowicz, Małgorzata; Pozowski, Andrzej; Kuciel-Lewandowska, Jadwiga

    2013-01-01

    The total removal of the larynx (total laryngectomy), performed in 1872 by the well-known Viennese surgeon Christian A. Theodor Billroth (1829–1894), was an epoch-making event in the history of surgery and laryngology. This paper presents the first surgeons who performed this operation. The first Pole who performed a total laryngectomy (1877) was Julian Kosiński (1833–1914), head of the Surgical Clinic of Imperial University Warsaw. It was the 14th operation of this kind in the world. Several...

  19. Anterior Approach Total Hip Replacement

    Medline Plus

    Full Text Available ... an anterior approach total hip replacement with the patient on a regular OR table supine. My name ... less invasive without being small incision surgery. Obese patients can be easier due to less distribution of ...

  20. Total anomalous pulmonary venous return

    Science.gov (United States)

    TAPVR; Total veins; Congenital heart defect - TAPVR; Cyanotic heart disease - TAPVR ... Fraser CD, Carberry KE. Congenital heart disease. In: Townsend CM Jr, Beauchamp RD, Evers BM, Mattox KL, eds. Sabiston Textbook of Surgery . 19th ed. Philadelphia, PA: Elsevier ...

  1. Total Knee Replacement for Women

    Medline Plus

    Full Text Available ... at Florida Orthopedic Institute in Tampa, Florida. Tonight I’ll be moderating a Zimmer Gender Solutions total ... the e-mail seen on your screen, and I’ll do my best to sift through those ...

  2. Total Knee Replacement for Women

    Medline Plus

    Full Text Available ... that we feel because of their health and age has the potential for a total knee to ... I can evaluate? Is there any cut-off age that you would put in regular polyethylene or ...

  3. Minimally Invasive Total Knee Arthroplasty

    Medline Plus

    Full Text Available ... Institute. We're going to be doing an MIS total knee arthroplasty with the Zimmer mobile bearing ... this point. And there is many recipes for MIS knee surgery as there are surgeons. What’s kind ...

  4. Total Product Life Cycle (TPLC)

    Data.gov (United States)

    U.S. Department of Health & Human Services — The Total Product Life Cycle (TPLC) database integrates premarket and postmarket data about medical devices. It includes information pulled from CDRH databases...

  5. A Choir for Total Communication.

    Science.gov (United States)

    Knapp, Ruth Ann

    1980-01-01

    The Total Communication Choir of the Saginaw, Michigan, public schools integrates deaf and hearing elementary and junior high students in music performance. All students both sign and sing. Methods used to instruct the choir are described. (SJL)

  6. Qualità totale e mobilità totale

    Directory of Open Access Journals (Sweden)

    Giuseppe Trieste

    2010-04-01

    Full Text Available FIABA ONLUS (Italian Fund for Elimination of Architectural Barriers was founded in 2000 with the aim of promoting a culture of equal opportunities and, above all, it has as its main goal to involve public and private institutions to create a really accessible and usable environment for everyone. Total accessibility, Total usability and Total mobility are key indicators to define quality of life within cities. A supportive environment that is free of architectural, cultural and psychological barriers allows everyone to live with ease and universality. In fact, people who access to goods and services in the urban context can use to their advantage time and space, so they can do their activities and can maintain relationships that are deemed significant for their social life. The main aim of urban accessibility is to raise the comfort of space for citizens, eliminating all barriers that discriminate people, and prevent from an equality of opportunity. “FIABA FUND - City of ... for the removal of architectural barriers” is an idea of FIABA that has already affected many regions of Italy as Lazio, Lombardy, Campania, Abruzzi and Calabria. It is a National project which provides for opening a bank account in the cities of referring, in which for the first time, all together, individuals and private and public institutions can make a donation to fund initiatives for the removal of architectural barriers within its own territory for a real and effective total accessibility. Last February the fund was launched in Rome with the aim of achieving a Capital without barriers and a Town European model of accessibility and usability. Urban mobility is a prerequisite to access to goods and services, and to organize activities related to daily life. FIABA promotes the concept of sustainable mobility for all, supported by the European Commission’s White Paper. We need a cultural change in management and organization of public means, which might focus on

  7. Total Liability for Excessive Harm

    OpenAIRE

    Cooter, Robert D; Porat, Ariel

    2005-01-01

    The harm that each individual causes others is unverifiable in some circumstances where the total harm caused by everyone is verifiable. For example, the environmental agency can often measure the total harm caused by pollution much easier than it can measure the harm caused by each individual polluter. In these circumstances, implementing the usual liability rules or externality taxes is impossible. We propose a novel solution: Hold each participant in the activity responsible for all of the...

  8. Total Liability for Excessive Harm

    OpenAIRE

    Cooter, Robert D; Porat, Ariel

    2004-01-01

    In many circumstances, the total harm caused by everyone is verifiable, and the harm caused by each individual is unverifiable. For example, the environmental agency can measure the total harm caused by pollution much easier than it can measure the harm caused by each individual polluter. In these circumstances, implementing the usual liability rules or externality taxes is impossible. We propose a novel solution: Hold each participant in the activity responsible for all of the excessive harm...

  9. Total synthesis of (-)-spinosyn A.

    Science.gov (United States)

    Mergott, Dustin J; Frank, Scott A; Roush, William R

    2004-08-17

    A convergent, highly stereoselective total synthesis of (-)-spinosyn A (1) is described. Key features of the synthesis include the transannular Diels-Alder reaction of macrocyclic pentaene 11 and the transannular Morita-Baylis-Hillman cyclization of 12 that generates tetracycle 26. The total synthesis of (-)-spinosyn A was completed by a sequence involving the highly beta-selective glycosidation reaction of 13 and glycosyl imidate 30. PMID:15173590

  10. The total charm cross section

    OpenAIRE

    R. Vogt

    2007-01-01

    We assess the theoretical uncertainties on the total charm cross section. We discuss the importance of the quark mass, the scale choice and the parton densities on the estimate of the uncertainty. We conclude that due to the small charm quark mass, which amplifies the effect of the other parameters in the calculation, the uncertainty on the total charm cross section is difficult to quantify.

  11. Total body water and total body potassium in anorexia nervosa

    International Nuclear Information System (INIS)

    In the ill hospitalized patient with clinically relevant malnutrition, there is a measurable decrease in the ratio of the total body potassium to total body water (TBK/TBW) and a detectable increase in the ratio of total exchangeable sodium to total exchangeable potassium (Nae/Ke). To evaluate body composition analyses in anorexia nervosa patients with chronic uncomplicated semistarvation, TBK and TBW were measured by whole body K40 counting and deuterium oxide dilution in 10 females with stable anorexia nervosa and 10 age-matched female controls. The ratio of TBK/TBW was significantly (p less than 0.05) higher in anorexia nervosa patients than controls. The close inverse correlation found in published studies between TBK/TBW and Nae/Ke together with our results suggest that in anorexia nervosa, Nae/Ke may be low or normal. A decreased TBK/TBW is not a good indicator of malnutrition in the anorexia nervosa patient. The use of a decreased TBK/TBW ratio or an elevated Nae/Ke ratio as a definition of malnutrition may result in inappropriate nutritional management in the patient with severe nonstressed chronic semistarvation

  12. Total body water and total body potassium in anorexia nervosa

    Energy Technology Data Exchange (ETDEWEB)

    Dempsey, D.T.; Crosby, L.O.; Lusk, E.; Oberlander, J.L.; Pertschuk, M.J.; Mullen, J.L.

    1984-08-01

    In the ill hospitalized patient with clinically relevant malnutrition, there is a measurable decrease in the ratio of the total body potassium to total body water (TBK/TBW) and a detectable increase in the ratio of total exchangeable sodium to total exchangeable potassium (Nae/Ke). To evaluate body composition analyses in anorexia nervosa patients with chronic uncomplicated semistarvation, TBK and TBW were measured by whole body K40 counting and deuterium oxide dilution in 10 females with stable anorexia nervosa and 10 age-matched female controls. The ratio of TBK/TBW was significantly (p less than 0.05) higher in anorexia nervosa patients than controls. The close inverse correlation found in published studies between TBK/TBW and Nae/Ke together with our results suggest that in anorexia nervosa, Nae/Ke may be low or normal. A decreased TBK/TBW is not a good indicator of malnutrition in the anorexia nervosa patient. The use of a decreased TBK/TBW ratio or an elevated Nae/Ke ratio as a definition of malnutrition may result in inappropriate nutritional management in the patient with severe nonstressed chronic semistarvation.

  13. Total 2004 annual report; TOTAL 2004 rapport annuel

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2004-07-01

    This annual report of the Group Total brings information and economic data on the following topics, for the year 2004: the corporate governance, the corporate social responsibility, the shareholder notebook, the management report, the activities, the upstream (exploration and production) and downstream (refining and marketing) operating, chemicals and other matters. (A.L.B.)

  14. Elective hemithyroidectomy during total laryngectomy

    Directory of Open Access Journals (Sweden)

    Soheyla Nikakhlagh

    2009-01-01

    Full Text Available Introduction: Routine hemithyroidectomy during total laryngectomy in the setting of advanced stage of laryngeal carcinoma without clear thyroid involvement remains a controversial issue. This study was conducted to assess the rate of thyroid gland involvement in the patients without obvious clinical involvement who were candidates for total laryngectomy. Materials and Methods: In this cross-sectional study, between 1994 and 2007, 186 patients who underwent total laryngectomy with ipsilateral hemithyroidectomy at Imam Khomeini hospital of Ahwaz Jondishapour university, were investigated for thyroid gland involvement. Results: Of 186 patients, 169 cases were men and 17 were women, with mean age of 63 years. Microscopic tissue study revealed tumor invasion to thyroid gland in 7 patients, all of them had clinically advanced disease. Among these patients, 5 cases had transglottic cancer and 2 cases had subglottic cancer. Moreover, 4 patients had thyroid cartilage invasion and in one patient pyriform sinus was involved. Conclusion: There may be no need for thyroidectomy in all total laryngectomy cases. We recommend hemithyroidectomy with isthmectomy during total laryngectomy only in cases with subglottic tumor extension, thyroid cartilage invasion, and pyriform sinus involvement.    

  15. TOTAL THYROIDECTOMY USING CAPSULAR DISSECTION

    Directory of Open Access Journals (Sweden)

    R. Moldovanu

    2008-01-01

    Full Text Available Total thyroidectomy can be performed with low rate of injuries of the recurrent laryngeal nerves and parathyroid glands, with appropriate techniques. The paper describes the technique of total thyroidectomy using capsular dissection and the indications of this operation. There are some steps which should be respected: good exposure of the thyroid gland, careful dissection of the superior pole using the avascular plane between superior pole and cricothyroid muscle, medial retraction of the gland, ligating the tertiary (third order branches of the inferior thyroid artery, near the surface of thyroid parenchyma. Using this type of dissection, the recurrent laryngeal nerves are protected, as well as the blood supply of the parathyroid glands. Conclusions: Total thyroidectomy using capsular dissection is the procedure of choice for multinodular goiter, because avoid the completion thyroidectomy for recurrence or occult thyroid cancer.

  16. Stereoselective Total Synthesis of Mycalamides

    Institute of Scientific and Technical Information of China (English)

    Masahiro Toyota

    2005-01-01

    @@ 1Introduction Mycalamides A (1a) and B (1b) are potent antiviral compounds from a New Zealand sponge of the genus Mycale. Apart from their antitumor property, mycalamide A (1a) exhibits immunosuppressive action by blocking T-cell activation in mice and is significantly more potent than FK-506 and cyclosporine A. Because of their intriguing biological activity, unique structures and scarce supply of these natural products, mycalamides A (1a) and B (1b) have attracted considerable attention as target molecules for total synthesis, and total, formal, or partial syntheses of this family of compounds have been reported[1,2].

  17. VOICE REHABILITATION FOLLOWING TOTAL LARYNGECTOMY

    Directory of Open Access Journals (Sweden)

    Balasubramanian Thiagarajan

    2015-03-01

    Full Text Available Despite continuing advances in surgical management of laryngeal malignancy, total laryngectomy is still the treatment of choice in advanced laryngeal malignancies. Considering the longevity of the patient following total laryngectomy, various measures have been adopted in order to provide voice function to the patient. Significant advancements have taken place in voice rehabilitation of post laryngectomy patients. Advancements in oncological surgical techniques and irradiation techniques have literally cured laryngeal malignancies. Among the various voice rehabilitation techniques available TEP (Tracheo oesophageal puncture is considered to be the gold standard. This article attempts to explore the various voice rehabilitation technique available with primary focus on TEP.

  18. Anterior Approach Total Hip Replacement

    Medline Plus

    Full Text Available ... and E-poly antioxidant-infused technology during a hip replacement through the anterior supine intramuscular approach. “OR- ... Dr. Keith Berend perform an anterior approach total hip replacement with the patient on a regular OR ...

  19. Total Synthesis of Propolisbenzofuran B†

    OpenAIRE

    Jones, Brian T.; Avetta, Christopher T.; Thomson, Regan J.

    2014-01-01

    The first total synthesis of propolisbenzofuran B, a bioactive natural product isolated from honeybee propolis resin, is reported. The convergent synthesis makes use of a silicon-tether controlled oxidative ketone–ketone cross-coupling and a novel benzofuran-generating cascade reaction to deliver the core structure of the natural product from readily prepared precursors.

  20. Minimally Invasive Total Knee Arthroplasty

    Medline Plus

    Full Text Available ... the NexGen® LPS-Flex Mobile and LPS-Mobile Bearing Knees March 5, 2009 Welcome to this "OR ... MIS total knee arthroplasty with the Zimmer mobile bearing knee. We invite all of you who have ...

  1. Total Knee Replacement for Women

    Medline Plus

    Full Text Available Zimmer Combines Gender Solutions technology May 27, 2009 Good evening. Welcome to “OR-Live” at Tampa General Hospital. My name is Steve Lyons, ... Tonight I’ll be moderating a Zimmer Gender Solutions total knee, performed by my partner, Dr. Ken ...

  2. Total Knee Replacement for Women

    Medline Plus

    Full Text Available Zimmer Combines Gender Solutions technology May 27, 2009 Good evening. Welcome to “OR-Live” at Tampa General Hospital. My name is ... Florida. Tonight I’ll be moderating a Zimmer Gender Solutions total knee, performed by my partner, Dr. ...

  3. Total Knee Replacement for Women

    Medline Plus

    Full Text Available ... Ken, here’s another question. “Do you utilize highly cross linked polyethylene for all your total knees or just in younger patients? I use the highly cross linked polyethylene in all the knees. I think ...

  4. Totally indefinite Euclidean quaternion fields

    OpenAIRE

    Cerri, Jean-Paul; Chaubert, Jérôme; Lezowski, Pierre

    2014-01-01

    We study the Euclidean property for totally indefinite quaternion fields. In particular, we establish the complete list of norm-Euclidean such fields over imaginary quadratic number fields. This enables us to exhibit an example which gives a negative answer to a question asked by Eichler. The proofs are both theoretical and algorithmic.

  5. Minimally Invasive Total Knee Arthroplasty

    Medline Plus

    Full Text Available ... NexGen® LPS-Flex Mobile and LPS-Mobile Bearing Knees March 5, 2009 Welcome to this "OR Live" ... re going to be doing an MIS total knee arthroplasty with the Zimmer mobile bearing knee. We ...

  6. Edge colouring by total labellings

    DEFF Research Database (Denmark)

    Brandt, Stephan; Rautenbach, D.; Stiebitz, M.;

    2010-01-01

    We introduce the concept of an edge-colouring total k-labelling. This is a labelling of the vertices and the edges of a graph G with labels 1, 2, ..., k such that the weights of the edges define a proper edge colouring of G. Here the weight of an edge is the sum of its label and the labels of its...... two endvertices. We define χ (G) to be the smallest integer k for which G has an edge-colouring total k-labelling. This parameter has natural upper and lower bounds in terms of the maximum degree Δ of G : ⌈ (Δ + 1) / 2 ⌉ ≤ χ (G) ≤ Δ + 1. We improve the upper bound by 1 for every graph and prove χ (G...

  7. CYPRINIDS TOTAL BLOOD PROTEINS DETERMINATION

    Directory of Open Access Journals (Sweden)

    TANŢI PATRICHE

    2013-07-01

    Full Text Available In aquaculture to get a high production is conditioned by awareness and keeping of an unaltered health condition of the biological material. To be aware of the health condition of the biological material in a fish farm allows us to establish the preventive measures required to prevent spreading of a disease and the treatment to be applied in case that a mass disease occurs. The level of the total protein in serum is, first of all, a synthetically indicator of the nutritional condition of the organism, presenting, at the same time, ample qualitative and quantitative variations depending on species, age, sex, stage of sexual maturity, water temperature and especially in correlation with the health condition of fish. Modification in value of the total protein point out some metabolic perturbations in fish body.

  8. Total sternectomy for malignant disease.

    Science.gov (United States)

    París, F; Blasco, E; Tarazona, V; Pastor, J; Zarza, A G; Padilla, J

    1980-09-01

    From 1972 to 1978, six total sternectomies for malignant disease of the sternum were carried out. The clinical data are summarized and the surgical technique is described. After sternectomy, the area of chest wall resection was repaired by suturing a sheet of silicone rubber to the edges of the defect and chest wall stability was assured by using one or two stainless steel struts. Finally the defect was covered with methylmethacrylate prepared and applied inthe operative field. The prosthetic material was shaped until curing by polymerization was complete. We discuss the advantages of this type of reconstruction, the technical details, the use of antibiotics, the surgical drainage, and the need for biopsy prior to carrying out a total sternectomy. PMID:7412352

  9. Outcome after total elbow arthroplasty

    DEFF Research Database (Denmark)

    Plaschke, Hans Christian; Thillemann, Theis M; Brorson, Stig;

    2015-01-01

    BACKGROUND: Total elbow arthroplasties (TEAs) are traditionally grouped into linked and unlinked design. The aim was to analyze the difference in clinical outcomes after TEA based on implant design and indication for surgery and to evaluate primary and revision TEAs. METHODS: A total of 167 TEAs...... (126 primary and 41 revision TEAs) in 141 patients were evaluated with patient-reported outcome measure by the Oxford Elbow Score (OES) and clinically assessed with the Mayo Elbow Performance Score (MEPS), range of motion (ROM), and standard radiographs. RESULTS: The mean follow-up was 10.5 years for...... primary and 7.5 years for revision TEAs. There was no difference in OES or MEPS between linked and unlinked primary TEAs. The OES score in the social-psychological domain was significantly lower in TEAs performed due to fracture (67) compared with rheumatoid arthritis (81; P = .025). ROM in extension...

  10. Total positivity in Markov structures

    OpenAIRE

    Fallat, Shaun; Lauritzen, Steffen; Sadeghi, Kayvan; Uhler, Caroline; Wermuth, Nanny; Zwiernik, Piotr

    2015-01-01

    We discuss properties of distributions that are multivariate totally positive of order two (MTP2) related to conditional independence. In particular, we show that any independence model generated by an MTP2 distribution is a compositional semigraphoid which is upward-stable and singleton-transitive. In addition, we prove that any MTP2 distribution satisfying an appropriate support condition is faithful to its concentration graph. Finally, we analyze factorization properties of MTP2 distributi...

  11. Diastereoselective Total Synthesis of (-)-Galiellalactone.

    Science.gov (United States)

    Kim, Taewoo; Han, Young Taek; An, Hongchan; Kim, Kyeojin; Lee, Jeeyeon; Suh, Young-Ger

    2015-12-18

    An enantioselective total synthesis of (-)-galiellalactone has been accomplished. The key features of the synthesis involve the highly stereoselective construction of the cis-trisubstituted cyclopentane intermediate by a Pd(0)-catalyzed cyclization, the stereospecific introduction of an angular hydroxyl group by Riley oxidation, and the efficient construction of the tricyclic system of (-)-galiellalactone via a combination of diastereoselective Hosomi-Sakurai crotylation and ring-closing metathesis (RCM). PMID:26544529

  12. Total solar eclipse 2001 - Angola

    Czech Academy of Sciences Publication Activity Database

    Marková, E.; Kotrč, Pavel; Křivský, L.; Bělík, M.; Dušek, J.

    Noordwijk : ESA Publication Division, 2002 - (Sawaya-Lacoste, H.), s. 245-248 [Solar Cycle and Space Weather Euroconference /2./. Vico Equense (IT), 24.09.2001-29.09.2001] R&D Projects: GA ČR GA205/01/0420 Institutional research plan: CEZ:AV0Z1003909 Keywords : total solar eclipse * white-light corona Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics

  13. Diverticulosis in total colonic aganglionosis

    International Nuclear Information System (INIS)

    Two infants with total colonic aganglionosis (TCA) extending into the distal part of the ileum are described. Considerable diagnostic delay occurred with the correct diagnosis established first at 3 and 8 months, respectively. Radiologic findings compatible with TCA such as prolonged barium retention, reflux into ileum following barium enema, and foreshortening of colon were not clearly evident initially. Both patients demonstrated multiple acquired colon diverticula which increased both in number and size during the period of observation. These diverticula are probably a late manifestation of the spastic state of the anganglionic colon. Thus demonstration of diverticula supplies a strong evidence of TCA in infants with intestinal obstruction. (orig.)

  14. Total Synthesis of the Ammosamides

    Science.gov (United States)

    Hughes, Chambers C.; Fenical, William

    2010-01-01

    The ammosamides A-C are chlorinated pyrrolo[4,3,2-de]quinoline metabolites isolated from the marine-derived Streptomyces strain CNR-698. The natural products, which possess a dense array of heteroatoms, were synthesized in 17–19 steps from 4-chloroisatin. That the five nitrogen atoms were introduced at the appropriate time and in a suitable oxidation state was key to the success of the total synthesis. Compared to synthetic deschloro ammosamide B, natural ammosamide B is much less susceptible to oxidative degradation. PMID:20131899

  15. Total eclipses of the sun

    CERN Document Server

    Zirker, Jack B

    2014-01-01

    Eclipses have captured attention and sparked curiosity about the cosmos since the first appearance of humankind. Having been blamed for everything from natural disasters to the fall of kings, they are now invaluable tools for understanding many celestial as well as terrestrial phenomena. This clear, easy-to-understand guide explains what causes total eclipses and how they can be used in experiments to examine everything from the dust between the planets to general relativity. A new chapter has been added on the eclipse of July 11, 1991 (the great Hawaiian eclipse). Originally published in 19

  16. Total filmless digital radiology service

    International Nuclear Information System (INIS)

    The completion of a comprehensive picture archiving and communication system (PACS) at Georgetown University Hospital has allowed us to identify a number of technical, administrative, personnel, and operational issues that will affect a total digital radiology service. With a hospital-wide digital imaging network system, computer simulation of communications and storage options, and economic modeling, we have developed a feasibility study and implementation strategy for the smooth transition to a nearly filmless radiology service over the next several years. This paper describes the technical and operational requirements for various database operations, workstations (used in diagnosis, review, and education), and communications. Site and installation planning, personnel training, and transition operations are discussed

  17. First total synthesis of Boehmenan

    Indian Academy of Sciences (India)

    Yamu Xia; Xiaoli Dai; Haixin Liu; Chen Chai

    2014-05-01

    The first total synthesis of dilignan Boehmenan has been achieved. A biomimetic oxidative coupling of the ferulic acid methyl ester in the presence of silver oxide is the crucial step in the synthesis sequence, generating the dihydrobenzofuran skeleton. Hydroxyl group was protected with DHP and reducted with LiAlH4 to afford the intermediate diol. The diol was condensated with the derivative of ferulic acid, then removed the protecting groups, to get Boehmenan. Meanwhile, a study on the ring-opening reaction of the intermediate dihydrobenzofuran neolignan under base conditions was described.

  18. Radiology of total hip replacement

    Energy Technology Data Exchange (ETDEWEB)

    Griffiths, H.J.; Lovelock, J.E.; McCollister Evarts, C.; Geyer, D.

    1984-06-01

    The radiology of total hip replacement (THR) and its complications is reviewed in conjunction with a long-term follow-up study on 402 patients with 501 prostheses. The indications, contraindications, biomechanics, and operative management of these patients is discussed. Clinical complications such as deep vein thrombosis, pulmonary embolism, and hemorrhage are mentioned. Postoperative infections including granulomatous pseudotumors, dislocations and fractures, true loosening of the prosthesis, and heterotopic bone formation (HBF) are discussed and illustrated. The importance of differentiating the lucent line from true loosening is stressed. Mechanical and other clinical complications which are largely ignored by radiologists are also discussed. The uses of arthrography and bone scanning are included.

  19. Solar total energy project Shenandoah

    Energy Technology Data Exchange (ETDEWEB)

    None

    1980-01-10

    This document presents the description of the final design for the Solar Total Energy System (STES) to be installed at the Shenandoah, Georgia, site for utilization by the Bleyle knitwear plant. The system is a fully cascaded total energy system design featuring high temperature paraboloidal dish solar collectors with a 235 concentration ratio, a steam Rankine cycle power conversion system capable of supplying 100 to 400 kW(e) output with an intermediate process steam take-off point, and a back pressure condenser for heating and cooling. The design also includes an integrated control system employing the supervisory control concept to allow maximum experimental flexibility. The system design criteria and requirements are presented including the performance criteria and operating requirements, environmental conditions of operation; interface requirements with the Bleyle plant and the Georgia Power Company lines; maintenance, reliability, and testing requirements; health and safety requirements; and other applicable ordinances and codes. The major subsystems of the STES are described including the Solar Collection Subysystem (SCS), the Power Conversion Subsystem (PCS), the Thermal Utilization Subsystem (TUS), the Control and Instrumentation Subsystem (CAIS), and the Electrical Subsystem (ES). Each of these sections include design criteria and operational requirements specific to the subsystem, including interface requirements with the other subsystems, maintenance and reliability requirements, and testing and acceptance criteria. (WHK)

  20. Employees in Total Quality Management

    Directory of Open Access Journals (Sweden)

    M. G. Matlhape

    2002-12-01

    Full Text Available Companies have become very disillusioned with Total Quality Management (TQM as a solution to their quality related problems. Part of the problem has been that companies' expectations from TQM is as a solution to their existing problems rather than as a new philosophy towards creating value for shareholders, employees, and customers. Employee involvement is usually the element in the TQM philosophy that is most difficult to manage. Central to employee participation within the TQM philosophy is teamwork. In the attempt to facilitate total quality management, this article explores specific South African challenges to achieving this. These areaffirmative action and divers ity management skills shortages, training and development low levels of employee well-being. Working with people requires fundamental understanding of the uniqueness of each individual with their own identity and set of preferences. It also requires an understanding of teams and the mechanisms of making a group of individuals work well or poorly together. This will assist managers to realise active participation, quality output from their workers through individualised, and team based motivational processes.

  1. Qualidade total: Um novo paradigma?

    Directory of Open Access Journals (Sweden)

    Suzana da Rosa Tolfo

    1999-01-01

    Full Text Available Nos últimos anos, o movimento para a implantação da Gestão da Qualidade Total vem crescendo ao redor do mundo. Em razão disso, há uma diversidade de ações realizadas com o nome de "Qualidade Total'. Uma revisão da teoria é complexa, porque existem muitos autores que tratam da questão. Eles escolhem diferentes perspectivas de análises (teóricas e empíricas e há dificuldades em se identificar um corpo conceitual. Há uma ampla difusão de modelos, ferramentas, técnicas, mercado e consultores. Essa popularidade, muitas vezes, faz com que determinadas organizações adotem essa forma de gestão do trabalho sem o conhecimento necessário das implicações que um modelo dessa ordem representa; especialmente no caso brasileiro, suscetível a proposições importadas. O presente artigo propõe um exame daquilo que os fundadores têm articulado sobre TQM, as principais críticas nesta direção e a avaliação de como vem sendo aplicadono nosso país.

  2. Total Value of Phosphorus Recovery.

    Science.gov (United States)

    Mayer, Brooke K; Baker, Lawrence A; Boyer, Treavor H; Drechsel, Pay; Gifford, Mac; Hanjra, Munir A; Parameswaran, Prathap; Stoltzfus, Jared; Westerhoff, Paul; Rittmann, Bruce E

    2016-07-01

    Phosphorus (P) is a critical, geographically concentrated, nonrenewable resource necessary to support global food production. In excess (e.g., due to runoff or wastewater discharges), P is also a primary cause of eutrophication. To reconcile the simultaneous shortage and overabundance of P, lost P flows must be recovered and reused, alongside improvements in P-use efficiency. While this motivation is increasingly being recognized, little P recovery is practiced today, as recovered P generally cannot compete with the relatively low cost of mined P. Therefore, P is often captured to prevent its release into the environment without beneficial recovery and reuse. However, additional incentives for P recovery emerge when accounting for the total value of P recovery. This article provides a comprehensive overview of the range of benefits of recovering P from waste streams, i.e., the total value of recovering P. This approach accounts for P products, as well as other assets that are associated with P and can be recovered in parallel, such as energy, nitrogen, metals and minerals, and water. Additionally, P recovery provides valuable services to society and the environment by protecting and improving environmental quality, enhancing efficiency of waste treatment facilities, and improving food security and social equity. The needs to make P recovery a reality are also discussed, including business models, bottlenecks, and policy and education strategies. PMID:27214029

  3. Application Of Total Quality Management In Library

    OpenAIRE

    Vilas A. Kale

    2013-01-01

    The paper focuses on the application of Total Quality Management in Library in different sub-titles such as Need for Quality Management, Total Quantity Management, Basic components of Total Quality Management, Key Elements in Total Quality Management, Total Quality Management and Libraries, Implementation of Total Quality Management in Library. Application of Total Quality Management in Libraries will provide a vital link for managerial decision makers.

  4. Demand: a total nuclear disarmament

    International Nuclear Information System (INIS)

    This bibliographical note presents a book, in which the authors make a plea for a total nuclear disarmament. They think that humanity cannot be found in competition, but in emulation, and examine how we can get rid of the nuclear bomb. They discuss the background of nuclear energy, state that nuclear weapons have always been useless and extremely dangerous, consider arms race as crazy and as a crime against humanity, recall that nuclear weapons already made numerous victims (Hiroshima, Nagasaki, nuclear tests), that they are a sword of Damocles over 7 billions human beings, that nuclear winter would be an apocalypse, that the Non Proliferation Treaty is a decoy. They discuss the political role of nuclear weapons, and outline that the only solution is their abolition. They discuss what has already been done and what is still to be done, and formulate a strategy for the future

  5. Complications after total hip replacement

    International Nuclear Information System (INIS)

    Complications seen after long-term follow-up examinations of total hip replacement should be treated immediately and completely. In the past decade a considerable increase in revisions has been noted. Radiographic assessment may be regarded as an effective means in diagnosing prosthetic complications from the surgeon's point of view. Examples are given. The difficulties in radiographic assessment of complications after cementless implanation or cemented prostheses without contrast media are mentioned. Prosthesis-related complications, such as mechanical loosening, infection with and without loosening, fatigue fractures and wear, fractures of the femur or pelvis, dislocations and surgical failures, are illustrated, as are clinical courses with gross loss of bone stock after repeated surgery and delayed revisions. Complications not related to the prosthesis such as periarticular ossification, muscle deficiencies, and nervous and vascular lesions are also explained using examples. (orig.)

  6. A total safety management model

    International Nuclear Information System (INIS)

    In nuclear organizations, quality and safety are inextricably linked. Therefore, the search for excellence means reaching excellence in nuclear safety. The International Atomic Energy Agency, IAEA, developed, after the Chernobyl accident, the organizational approach for improving nuclear safety based on the safety culture, which requires a framework necessary to provide modifications in personnel attitudes and behaviors in situations related to safety. This work presents a Total Safety Management Model, based on the Model of Excellence of the Brazilian Quality Award and on the safety culture approach, which represents an alternative to this framework. The Model is currently under validation at the Nuclear Engineering Institute, in Rio de Janeiro, Brazil, and the results of its initial safety culture self assessment are also presented and discussed. (author)

  7. Sociologist in the total institution

    Directory of Open Access Journals (Sweden)

    Krstić Željko

    2010-01-01

    Full Text Available On the basis of empirical experience from practical work this paper discusses the real place and role of the sociologist in the prison, as a total institution, where sociologists are employed as educators, along with other professions (psychologists, educationalists, social workers, etc., and usually closely cooperating with lawyers. According to the current work regulations, and on the basis of practice so far, the sociologist can work as classical educator, to be in charge of educational groups of inmates, work in the reception department on assessing incoming inmates, and to organize inmates' leisure time by directing them towards pro-social and creative activities (music, painting, reading, etc.. New reform trends in working with inmates suggest new work methods, such as creative workshops, counselling in the sphere of substance abuse and dependency, or expert teams in working with minors. In the prison, the sociologist is indispensable as a researcher of criminal activities.

  8. Total quality management implementation guidelines

    Energy Technology Data Exchange (ETDEWEB)

    1993-12-01

    These Guidelines were designed by the Energy Quality Council to help managers and supervisors in the Department of Energy Complex bring Total Quality Management to their organizations. Because the Department is composed of a rich mixture of diverse organizations, each with its own distinctive culture and quality history, these Guidelines are intended to be adapted by users to meet the particular needs of their organizations. For example, for organizations that are well along on their quality journeys and may already have achieved quality results, these Guidelines will provide a consistent methodology and terminology reference to foster their alignment with the overall Energy quality initiative. For organizations that are just beginning their quality journeys, these Guidelines will serve as a startup manual on quality principles applied in the Energy context.

  9. Total quality management program planning

    Energy Technology Data Exchange (ETDEWEB)

    Thornton, P.T.; Spence, K.

    1994-05-01

    As government funding grows scarce, competition between the national laboratories is increasing dramatically. In this era of tougher competition, there is no for resistance to change. There must instead be a uniform commitment to improving the overall quality of our products (research and technology) and an increased focus on our customers` needs. There has been an ongoing effort to bring the principles of total quality management (TQM) to all Energy Systems employees to help them better prepare for future changes while responding to the pressures on federal budgets. The need exists for instituting a vigorous program of education and training to an understanding of the techniques needed to improve and initiate a change in organizational culture. The TQM facilitator is responsible for educating the work force on the benefits of self-managed work teams, designing a program of instruction for implementation, and thus getting TQM off the ground at the worker and first-line supervisory levels so that the benefits can flow back up. This program plan presents a conceptual model for TQM in the form of a hot air balloon. In this model, there are numerous factors which can individually and collectively impede the progress of TQM within the division and the Laboratory. When these factors are addressed and corrected, the benefits of TQM become more visible. As this occurs, it is hoped that workers and management alike will grasp the ``total quality`` concept as an acceptable agent for change and continual improvement. TQM can then rise to the occasion and take its rightful place as an integral and valid step in the Laboratory`s formula for survival.

  10. Dosimetry of total body irradiation

    International Nuclear Information System (INIS)

    In the treatment of disseminated malignancies an improvement in the curability and reduction of complication rates require high precision total body irradiation (TBI) and correct reporting of relevant treatment parameters. Optimal TBI dosimetry is the basis. Radiooncological and radiobiological requirements as well as the special physical situation have to be considered. To review the efforts of medical physicists, highlights from TBI workshops and publications are summarized. Additionally, dosimetric data from 34 European radiooncological centres contributing to the recent ESTRO inquiry on TBI are analysed. The topics are: absorbed dose and dose monitor calibration, determination of absolute and relative doses, dose ratios, attenuation data and heterogeneity corrections; TBI dose calculation methods regarding patient position, beam incidence, body shape and thickness, lung size and density; methods of TBI treatment planning including calculated dose modification and of TBI quality assurance. In conclusion, the following recommendations can be given: TBI dosimetry shall be performed under TBI conditions, close to the real treatment situation. The absorbed dose to water must be determined. The dose monitor should be calibrated against dose measurements at the centre of a water equivalent phantom of TBI equivalent size and typical thickness. Photon fluence profiles have to be measured with small phantoms. Influences on the local dose must be investigated systematically. A reproducible AP/PA TBI technique should be used. The TBI dose shall be specified to mid-abdomen and reported in units of gray. The single and total dose and the dose rate to the lungs, the number of fractions and the treatment time schedule must be stated. In vivo dosimetry is required if non-reliable TBI techniques are used. An international TBI dosimetry intercomparison could assist these efforts to improve the treatment of acute leukaemia. (author). 89 refs, 3 figs, 13 tabs

  11. Hypermnesia and total retrieval time.

    Science.gov (United States)

    Mulligan, Neil W

    2006-05-01

    Recall performance sometimes improves over repeated recall attempts, a phenomenon dubbed hypermnesia. A critical theoretical issue is whether hypermnesia is due to repeated testing per se or increased retrieval time. The present experiments investigated by contrasting five testing conditions. All participants were presented with the same study list followed by either two shorter recall tests or a single longer test. In the multiple test conditions, the tests were either separated by a (filled) 7-minute interval (the multiple-split condition), or presented consecutively, with no break (the multiple-immediate condition). In the single test conditions, the test either began at the start of the recall session, after a (filled) 7-minute delay, or with a 7-minute interruption inserted in the middle. The multiple-split condition produced more reminiscence and hypermnesia than the multiple-immediate condition. More importantly, the multiple-split condition produced greater cumulative recall than any of the other conditions (which did not differ among themselves). That is, single and repeated recall tests of equal total duration are not functionally equivalent. PMID:16766451

  12. Total Petroleum Hydrocarbons (TPH): ToxFAQs

    Science.gov (United States)

    ... a state: This map displays locations where Total Petroleum Hydrocarbons (TPH) is known to be present. On ... I get more information? ToxFAQs TM for Total Petroleum Hydrocarbons (TPH) ( Hidrocarburos Totales de Petróleo (TPH) ) August ...

  13. Photochemical [2+2] cycloaddition of the olefinic double bonds in the supramolecular rectangle [Ru46-p-cymene)4(μ-oxalato)2(μ-4,4′-bipyridylethylene)2]4+

    OpenAIRE

    Barry, Nicolas P. E.; Therrien, Bruno

    2010-01-01

    Self-assembly of 4,4′-bipyridylethylene (bpe) bidentate connector with the dinuclear arene ruthenium clip [Ru2(η6-p-cymene)2(μ-oxalato)Cl2] in the presence of silver triflate affords the cationic organometallic rectangle [Ru4(η6-p-cymene)4(μ-oxalato)2(μ-bpe)2]4+ ([1][CF3SO3]4). Upon UV irradiation of a methanol solution of [1]4+, dimerisation of the olefinic double bonds of the two parallel bpe ligands occurs, thus giving rise to the [2+2] cycloaddition derivative [Ru4(η6-p-cymene)4(μ-oxalato...

  14. Influence of extraction type on the total phenolics, total flavonoids and total colour change of different varieties of fig extracts

    OpenAIRE

    Jokić, Stela; MUJIĆ, Ibrahim; Bucić-Kojić, Ana; Velić, Darko; Bilić, Mate; Planinić, Mirela; Lukinac, Jasmina

    2014-01-01

    The study examined the influence of ultrasound-assisted extraction and solid-liquid extraction with 80% of aqueous ethanol solution on the total phenolics, total flavonoids and total colour change of extracts from five different varieties of figs (Bjelica, Termenjača, Crnica, Bružetka bijela and Šaraguja). The total phenolic content was determined by using Folin Ciocalteau assay. The content of total flavonoids was measured spectrophotometrically by using the aluminium chloride colourimetric ...

  15. Cataractogenesis after total body irradiation

    International Nuclear Information System (INIS)

    Purpose: To evaluate the prognostic factors and the ophthalmologic follow-up on cataract formation following total body irradiation (TBI) prior to bone marrow transplantation (BMT). Methods and Materials: Between 1980 and 1992, 494 patients were referred to our department for TBI prior to BMT. The mean age was 32 ± 11 (median: 32, range: 2-63) years and the male to female ratio was 1.6 (304:190). The majority of patients were treated for acute leukemia (lymphoblastic, n = 177, 36%; or nonlymphoblastic, n = 139, 28%); 80 (16%) for chronic myeloid leukemia, 60 (12%) for non-Hodgkin's lymphoma, 23 (5%) for multiple myeloma, and 15 (3%) for other malignancies. Two hundred and fifty-four (51%) patients were grafted in the first complete remission (CR), 118 (24%) in second CR. Allogeneic BMT was performed in 210 (43%) patients, and autologous BMT in 284 (57%). Methotrexate combined to steroids (n = 47, 22%) or to cyclosporine (n = 163, 78%) was administered for graft-versus-host disease (GvHD) prophylaxis. In 188 patients (38%), heparin was used in the prevention of veno-occlusive disease (VOD) of the liver. Furthermore, steroid administration was registered in 223 patients (45%). The conditioning chemotherapy consisted of cyclophosphamide (Cy) alone in 332 (67%) patients. Total-body irradiation was administered either in single dose (STBI; 10 Gy in 1 day, n = 291) or in six fractions (FTBI; 12 Gy over 3 consecutive days, n = 203) before BMT. The mean instantaneous dose rate was 0.0574 ± 0.0289 Gy/min (0.024-0.1783). It was < 0.048 Gy/min in 157 patients (LOW group), ≥ 0.048 Gy/min and < 0.09 Gy/min in 301 patients (MEDIUM group), and ≥ 0.09 Gy/min in 36 patients (HIGH group). Results: When considering all patients, 42 (8.5%) patients developed cataracts after 13 to 72 months (median: 42 months) with a 5-year estimated cataract incidence (ECI) of 23%. Thirty-three (11.3%) out of 291 patients in the STBI group, and 9 (4.4%) out of 203 patients in the FTBI group

  16. Towards the total synthesis of Stawamycin. Synthesis of C11-C21 fragment

    OpenAIRE

    Dias Luiz C.; Jardim Luciana S. A.; Ferreira Andrea A.; Soarez Helena U.

    2001-01-01

    The carbocyclic (C11-C21) fragment of Stawamycin has been prepared by a sequence involving 11 steps (10% overall yield) from methyl (R)-(-)-3-hydroxy-2-methylpropionate. Key steps are Pd-catalyzed Stille coupling reaction between a vinyl iodide and a vinylstannane followed by an intramolecular Diels-Alder cycloaddition reaction to afford the desired adduct as the major isomer together with three other possible adducts in 78% overall yield.

  17. A Hierarchy of Totally Ordered Multicasts

    OpenAIRE

    Wilhelm, U. G.; Schiper, A

    1995-01-01

    The increased interest in protocols that provide a total order on message delivery has led to several different definitions of total order. In this paper we investigate these different definitions and propose a hierarchy that helps to better understand the implications of the different possibilities in terms of guarantees and communication cost. We identify two definitions: {\\em weak total order} and {\\em strong total order}, which are at the extremes of the proposed hierarchy, and incorpor...

  18. I. Developing methods for the analysis of chemistry students' inscriptions, II. Exploring the regioselectivity of 1,3-dipolar cycloadditions of munchnones, III. Stereochemical investigations of C-H activation reactions involving germylene and stannylene/aryl iodide reagents

    Science.gov (United States)

    Kiste, Alan L.

    I. Analyzing and comparing student-generated inscriptions in chemistry is crucial to gaining insight into students' understanding about chemistry concepts. Thus, we developed two methods of analyzing student-generated inscriptions: features analysis and thematic analysis. We have also demonstrated how these methods are able to discern differences between both how students inscribe their understandings and the content of those inscriptions, regardless of (1) how those inscriptions were created (i.e. computer vs. pencil-and-paper), (2) the nature of the inscriptions (verbal vs. pictorial), and (3) the expertise of the students. The ability to analyze inscriptions regardless of the medium allows the examination of multiple inscriptions in educational research applications as well as in the design and development of educational materials. Also, inscriptions can be compared across contexts, allowing the comparison of student-generated inscriptions derived from various educational interventions. Finally, the ability to compare inscriptions regardless of the level of expertise allows novice/expert comparisons as well as longitudinal comparison over time. II. Predicting the regiochemistry of 1,3-dipolar cycloadditions of munchnones and acetylenic dipolarophiles is difficult based on frontier molecular orbital theory (FMO) alone. We have proposed that, in addition to FMO considerations, steric factors influencing the non-covalent interactions between reactive centers in the transition state also influence the regioselectivity of these reactions. We have developed a scheme to use a tether-based regiocontrol strategy to synthesize 2,4-disubstituted pyrroles using N-(2-thiazolinyl) secondary amino acid derivatives. Attempts to synthesize these amino acid derivatives have been, so far, unsuccessful. III. To provide additional information about the mechanism of C-H activation reactions of stannylenes and germylenes, and to demonstrate the utility of these reactions, we explored

  19. TOTAL GLOBAL DOMINATION IN FUZZY GRAPH

    OpenAIRE

    Rohini, R.; P.Gladyis; C. V. R. Harinarayanan

    2014-01-01

    Let G be a fuzzy graph without isolated nodes. A subset D of V is said to be a total dominating set if every node in V is dominated by a node in D. A total dominating set D of a graph G= (V,E ) is a total global fuzzy dominating set (t.g.f.d. set) if D is also a total dominating set of G . The total global fuzzy domination number γtgf(G) of G is the minimum cardinality of a t.g.f.d. set for some classes of fuzzy graphs and obtain bounds for the same.

  20. Total Productive Maintenance at Paccar INC

    OpenAIRE

    Ştefan Farkas

    2010-01-01

    This paper reports the application of total productive maintenance method at Paccar Inc. truck’s plant in Victoria, Australia. The total productive maintenance method and total productive maintenance house are presented. The global equipment effectiveness is computed and exemplified. The production structure and organising maintenance are presented. Resultas of the variation of global equipment effectiveness and autonomous maintenance in a two weeks period of time are reported.

  1. Total Productive Maintenance at Paccar INC

    Directory of Open Access Journals (Sweden)

    Ştefan Farkas

    2010-06-01

    Full Text Available This paper reports the application of total productive maintenance method at Paccar Inc. truck’s plant in Victoria, Australia. The total productive maintenance method and total productive maintenance house are presented. The global equipment effectiveness is computed and exemplified. The production structure and organising maintenance are presented. Resultas of the variation of global equipment effectiveness and autonomous maintenance in a two weeks period of time are reported.

  2. Patient Matched Instruments and Total Knee System

    Medline Plus

    Full Text Available Smith & Nephew Technologies: VISIONAIRE™ Patient Matched Instruments and LEGION™ Total Knee System You must have Javascript enabled in your web browser. View Program Transcript Click ...

  3. Total pollution effect of urban surface runoff.

    Science.gov (United States)

    Luo, Hongbing; Luo, Lin; Huang, Gu; Liu, Ping; Li, Jingxian; Hu, Sheng; Wang, Fuxiang; Xu, Rui; Huang, Xiaoxue

    2009-01-01

    For pollution research with regard to urban surface runoff, most sampling strategies to date have focused on differences in land usage. With single land-use sampling, total surface runoff pollution effect cannot be evaluated unless every land usage spot is monitored. Through a new sampling strategy known as mixed stormwater sampling for a street community at discharge outlet adjacent to river, this study assessed the total urban surface runoff pollution effect caused by a variety of land uses and the pollutants washed off from the rain pipe system in the Futian River watershed in Shenzhen City of China. The water quality monitoring indices were COD (chemical oxygen demand), TSS (total suspend solid), TP (total phosphorus), TN (total nitrogen) and BOD (biochemical oxygen demand). The sums of total pollution loads discharged into the river for the four indices of COD, TSS, TN, and TP over all seven rainfall events were very different. The mathematical model for simulating total pollution loads was established from discharge outlet mixed stormwater sampling of total pollution loads on the basis of four parameters: rainfall intensity, total land area, impervious land area, and pervious land area. In order to treat surface runoff pollution, the values of MFF30 (mass first flush ratio) and FF30 (first 30% of runoff volume) can be considered as split-flow control criteria to obtain more effective and economical design of structural BMPs (best management practices) facilities. PMID:19999964

  4. Generalized gravitational entropy from total derivative action

    Science.gov (United States)

    Dong, Xi; Miao, Rong-Xin

    2015-12-01

    We investigate the generalized gravitational entropy from total derivative terms in the gravitational action. Following the method of Lewkowycz and Maldacena, we find that the generalized gravitational entropy from total derivatives vanishes. We compare our results with the work of Astaneh, Patrushev, and Solodukhin. We find that if total derivatives produced nonzero entropy, the holographic and the field-theoretic universal terms of entanglement entropy would not match. Furthermore, the second law of thermodynamics could be violated if the entropy of total derivatives did not vanish.

  5. Generalized Gravitational Entropy from Total Derivative Action

    CERN Document Server

    Dong, Xi

    2015-01-01

    We investigate the generalized gravitational entropy from total derivative terms in the gravitational action. Following the method of Lewkowycz and Maldacena, we find that the generalized gravitational entropy from total derivatives vanishes. We compare our results with the work of Astaneh, Patrushev, and Solodukhin. We find that if total derivatives produced nonzero entropy, the holographic and the field-theoretic universal terms of entanglement entropy would not match. Furthermore, the second law of thermodynamics could be violated if the entropy of total derivatives did not vanish.

  6. Timing the total reflection of light

    International Nuclear Information System (INIS)

    We have identified for the first time the absolute delay at total reflection, envisioned by Newton. We show that there are in fact two divergent Wigner delays, depending on the polarisation of the incident light. These measurements give a new insight on the passage from total reflection to refraction

  7. Total cardiovascular disease risk assessment: a review.

    LENUS (Irish Health Repository)

    Cooney, Marie Therese

    2011-09-01

    The high risk strategy for the prevention of cardiovascular disease (CVD) requires an assessment of an individual\\'s total CVD risk so that the most intensive risk factor management can be directed towards those at highest risk. Here we review developments in the assessment and estimation of total CVD risk.

  8. Sexuality after total vs. subtotal hysterectomy

    DEFF Research Database (Denmark)

    Zobbe, Vibeke Bahn; Gimbel, Helga Margrethe Elisabeth; Andersen, Birthe Margrethe;

    2004-01-01

    The effect of hysterectomy on sexuality is not fully elucidated and until recently total and subtotal hysterectomies have only been compared in observational studies.......The effect of hysterectomy on sexuality is not fully elucidated and until recently total and subtotal hysterectomies have only been compared in observational studies....

  9. A note on totally normal spaces

    International Nuclear Information System (INIS)

    In this note we give the necessary and sufficient condition for a topological space X such that the product space X x Y is totally normal for any (non discrete) metric space Y, and we show that a totally normal p-space need not be a perfectly normal in general, which makes Theorem 2 doubtful. (author). 6 refs

  10. Simultaneous and staged bilateral total hip arthroplasty

    DEFF Research Database (Denmark)

    Lindberg-Larsen, Martin; Joergensen, Christoffer Calov; Husted, Henrik;

    2013-01-01

    Bilateral total hip arthroplasty (BTHA) and bilateral simultaneous total hip arthroplasty (BSTHA) are done increasingly. Previous studies evaluating outcomes after bilateral procedures have found different results. The aim of this study was to investigate length of hospital stay (LOS), 30 days...

  11. 75 FR 22418 - FHA TOTAL Mortgage Scorecard

    Science.gov (United States)

    2010-04-28

    ... URBAN DEVELOPMENT FHA TOTAL Mortgage Scorecard AGENCY: Office of the Chief Information Officer, HUD... samples at FHA's request, and appeals in writing for loss of privilege to use the scorecard. DATES... following information: Title of Proposal: FHA TOTAL Mortgage Scorecard. OMB Approval Number: 2502-0556....

  12. Comparison of Recent Total Irradiance Measurements

    Science.gov (United States)

    Helizon, R.; Pap, J.

    2002-12-01

    Total solar irradiance has been measured since 1978 from various satellites. Since the absolute accuracy of the current irradiance measurements is about 0.2%, one needs to compile composite irradiance time series to study long-term changes and to establish whether there are any secular variations over the last two and half decades. In this paper we compare the UARS/ACRIM II and SOHO/VIRGO total irradiance data as well as the SOHO/VIRGO and ACRIM III total irradiance. Our main goal is to validate the newly processed ACRIM II total irradiance. Comparison of the SOHO/VIRGO and ACRIM III data will also help to establish whether the high total irradiance values for the maximum of solar cycle 23 represent real solar, rather than, instrumental events.

  13. Regio and stereoselectivity in ionic cycloadditions

    Indian Academy of Sciences (India)

    Venkatachalam Tamilmani; Durairajan Senthilnathan; Ponnambalam Venuvanalingam

    2008-03-01

    Acridizinium cation (ACR) and 2,3-dimethylisoquinolinium ion (DMIQ) undergo [2 + 4+] addition with dienophiles methyl vinyl ether (MVE) and propylene (PY) and the addition takes place across the diene unit containing the cationic centre and the dienophile acts as the electron donor. These reactions have two regiochemical paths and in each of them two possible stereo adducts could be formed. DFT calculations performed at B3LYP/6-31G(d) level have shown that the reactions pass through concerted mechanism and the TSs are highly asynchronous. Methoxy group in the dienophile can take up cis or trans orientation with respect to the double bond and in that trans orientation of the methoxy group is preferred. Calculations further show that syn 2 adduct is kinetically and thermodynamically more favoured in both the reactions in excellent agreement with the experimental observations. ACR is found to be more reactive than DMIQ as a diene and as a dienophile MVE is found to be more reactive than PY. Computed bond orders establish that the syn 2 transition states are the most `reactant’ like. Though the reactions have both electrostatic control and frontier orbital control the former dominates in the initial stages of the reaction.

  14. Total synthesis of amiclenomycin, an inhibitor of biotin biosynthesis.

    Science.gov (United States)

    Mann, Stéphane; Carillon, Sophie; Breyne, Olivier; Marquet, Andrée

    2002-01-18

    We describe the first synthesis of amiclenomycin, a natural product that has been found to inhibit biotin biosynthesis and, as a consequence, to exhibit antibiotic properties. Structure 1, with a trans relationship between the ring substituents. had previously been proposed for amiclenomycin on the basis of its 1H NMR spectrum. We have prepared the trans and cis isomers 1 and 2 by unequivocal routes and we conclude that the natural product is in fact the cis isomer 2. The properly substituted cyclohexadienyl rings were constructed first. A cycloaddition reaction between 1,2-di(phenylsulfonyl)ethylene and the N-allyloxycarbonyl diene 13, followed by reductive elimination of the phenylsulfinyl groups, gave the cis isomer 15. To obtain the trans isomer, the O-trimethylsilyl diene was used to give the cis hydroxylated Diels-Alder adduct 33, which was transformed into the corresponding trans amino derivative by means of a Mitsunobu reaction. The L-alpha-amino acid functionality was introduced by means of a Strecker reaction on the aldehydes 16 and 42, followed by enzymatic hydrolysis with immobilised pronase. PMID:11843156

  15. Total dominator chromatic number of a graph

    Directory of Open Access Journals (Sweden)

    Adel P. Kazemi

    2015-06-01

    Full Text Available Given a graph $G$, the total dominator coloring problem seeks a proper coloring of $G$ with the additional property that every vertex in the graph is adjacent to all vertices of a color class. We seek to minimize the number of color classes. We initiate to study this problem on several classes of graphs, as well as finding general bounds and characterizations. We also compare the total dominator chromatic number of a graph with the chromatic number and the total domination number of it.

  16. (d,1)-total labelling of graphs

    OpenAIRE

    Havet, Frédéric; Yu, Min-Li

    2002-01-01

    A $(d,1)$-total labelling of a graph $G$ is an assignment of integers to $V(G)\\cup E(G)$ such that: (i) any two adjacent vertices of $G$ receive distinct integers, (ii) any two adjacent edges of $G$ receive distinct integers, and (iii) a vertex and its incident edge receive integers that differ by at least $d$ in absolute value. The {\\it span} of a $(d,1)$-total labelling is the maximum difference between two labels. The minimum span of a $(d,1)$-total labelling of $G$ is denoted by $\\lambda_...

  17. Waardenburg's syndrome associated with total aganglionosis.

    OpenAIRE

    Farndon, P A; Bianchi, A.

    1983-01-01

    A Pakistani child of consanguineous parents had signs of Waardenburg's syndrome and total intestinal aganglionosis. This association seems to be a distinct clinical entity with an autosomal recessive mode of inheritance.

  18. Patient Matched Instruments and Total Knee System

    Medline Plus

    Full Text Available Smith & Nephew Technologies: VISIONAIRE™ Patient Matched Instruments and LEGION™ Total Knee System You must have Javascript enabled in your web browser. View Program Transcript Click Here to view the OR-Live, Inc. Privacy Policy and Legal ...

  19. Enantioselective Total Synthesis of (+)-Gliocladin C

    OpenAIRE

    Overman, Larry E.; Shin, Youseung

    2007-01-01

    The first total synthesis of gliocladin C, a fungal-derived marine alkaloid containing a rare trioxopiperazine fragment, is reported. This asymmetric synthesis establishes the absolute configuration of this structurally novel natural product.

  20. Concise Enantiospecific Total Synthesis of Tubingensin A

    OpenAIRE

    Goetz, Adam E.; Silberstein, Amanda L.; Corsello, Michael A.; Garg, Neil K.

    2014-01-01

    We report the enantiospecific total synthesis of (+)-tubingensin A. Our synthesis features an aryne cyclization to efficiently introduce the vicinal quaternary stereocenters of the natural product and proceeds in only nine steps (longest linear sequence) from known compounds.

  1. Total Knee System with Patient Matched Instrumentation

    Medline Plus

    Full Text Available LEGION™ Total Knee System with VISIONAIRE™ Patient Matched Instrumentation You must have Javascript enabled in your web browser. View Program Transcript Click Here to view the OR-Live, Inc. ...

  2. Total Synthesis of (±)-Hibiscone C

    OpenAIRE

    Ungureanu, Sinziana; Meadows, Maggie; Smith, Joel; Duff, David B.; Burgess, James M.; Goess, Brian C.

    2011-01-01

    A total synthesis of (±)- hibiscone C, one member of the furanosteroid family of natural products that also includes viridin and wortmannin, is reported. Two new pathways for formation of the key diacyl furan subunit are described.

  3. US-Total Electron Content Product (USTEC)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The US Total Electron Content (US-TEC) product is designed to specify TEC over the Continental US (CONUS) in near real-time. The product uses a Kalman Filter data...

  4. Total Hip Replacement (Arthroplasty) (Beyond the Basics)

    Science.gov (United States)

    ... stiffening caused by extra bone formation, also called heterotopic ossification, is a process in which some soft ... replacement (prosthetic) parts, with the goal of relieving pain and improving function. ● Most patients require total hip ...

  5. NESDIS Blended Total Precipitable Water (TPW) Products

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The blended Total Precipitable Water (TPW) product is derived from multiple sensors/satellites. The Percentage of TPW normal (PCT), or TPW anomaly, shows the...

  6. Total renewable energy self-sufficiency strategy

    International Nuclear Information System (INIS)

    To meet required electrical power and transportation fuel, a total renewable energy self-sufficiency strategy needs to be envisaged that will not add to the degradation of our environment. (author). 6 refs., 2 tabs

  7. The total plasmatic estriol on normal gestation

    International Nuclear Information System (INIS)

    The total plasmatic estriol in normal pregnants was determinated by radioimmunological method using estriol labelled with sup(125)I. The obtained results presented similar results in comparison with methods using sup(19)C and sup(3)H. (author)

  8. TOTAL REWARDS MODEL IN ROMANIAN COMPANIES

    Directory of Open Access Journals (Sweden)

    Elena-Sabina HODOR

    2014-04-01

    Full Text Available Total Rewards Management is a subject of major importance for companies, because, by using models for this, firms can achieve their objectives of high performance. In order to analyse a validated total rewards model in Romanian Accounting and Consulting Companies, it is used The WorldatWork Total Rewards Model, which depict what contributes to applicant attraction and employee motivation and retention. Thus, the methodology of the previous survey is adjusted to the local context. The conclusions for the methodological aspects illustrate that the present research involves three strategic steps in order to achieve the objectives presented: the analysis of organizational environment of the companies from the sample, checking if Total Rewards Model proposed in the previous research is applicable for the same romanian companies from the previous survey, the analysing of the differences between results, and, if necessary, the adaptation of the model for Romania.

  9. The First Total Synthesis of Isoliquiritin

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A first total synthesis of isoliquiritin was accomplished starting from p-hydroxy- benzaldehyde and 2,4-dihydroxyacetylphenone. The key step is condensation reaction. In synthetic process need not protect the hydroxy group of reacting substance.

  10. ROE Total Nitrogen Deposition 1989-1991

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset identifies the amount of wet, dry, and total deposition of nitrogen in kilograms per hectare from 1989 to 1991 at a set of point locations across the...

  11. Total lymphoid irradiation in alloimmunity and autoimmunity

    Energy Technology Data Exchange (ETDEWEB)

    Strober, S.

    1987-12-01

    Total lymphoid irradiation has been used as an immunosuppressive regimen in autoimmune disease and organ transplantation. The rationale for its use originated from studies of patients with Hodgkin disease, in whom this radiotherapy regimen was noted to induce profound and long-lasting immune suppression and yet was well tolerated, with few long-term side effects. Total lymphoid irradiation is a unique immunosuppressive regimen that produces a selective (and long-lasting) reduction in the number and function of helper T cells and certain subsets of B cells. Conventional immunosuppressive drugs show little selectivity, and their effects are short-lived. The most important aspect of total lymphoid irradiation is the potential for achieving transplantation tolerance and permanent remissions in autoimmune disease in laboratory animals. Attempts are being made to achieve similar goals in humans given total lymphoid irradiation, so that immunosuppressive drugs can be ultimately withdrawn from transplant recipients and patients with lupus nephritis. 28 references.

  12. ROE Total Nitrogen Deposition 2011-2013

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset identifies the amount of wet, dry, and total deposition of nitrogen in kilograms per hectare from 2011 to 2013 at a set of point locations across the...

  13. ROE Total Sulfur Deposition 1989-1991

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset identifies the amount of wet, dry, and total deposition of sulfur in kilograms per hectare from 1989 to 1991 at a set of point locations across the...

  14. A scheme for total quantum teleportation

    OpenAIRE

    DelRe, E.; Crosignani, B.; Di Porto, P.

    1999-01-01

    We address the issue of totally teleporting the quantum state of an external particle, as opposed to studies on partial teleportation of external single-particle states, total teleportation of coherent states and encoded single-particle states, and intramolecular teleportation of nuclear spin states. We find a set of commuting observables whose measurement directly projects onto the Bell-basis and discuss a possible experiment, based on two-photon absorption, allowing, for the first time, tot...

  15. A strategic zone for Total's future

    International Nuclear Information System (INIS)

    In 1997, the Total company investments in the Middle East reached 1.2 billions of French Francs. This region is considered as a major growth zone by the French group. This paper summarizes the Total's participations in oil and gas activities and partnerships of Middle East countries (Abu Dhabi, Dubai, Oman, Qatar, Yemen): exploration, production, development, contracts, permits, technical assistance etc.. (J.S.)

  16. Postoperative Autologous Reinfusion in Total Knee Replacement

    OpenAIRE

    A. Crescibene; Martire, F.; Gigliotti, P.; Rende, A.; Candela, M

    2015-01-01

    Surgeries for total knee replacement (TKR) are increasing and in this context there is a need to develop new protocols for management and use of blood transfusion therapy. Autologous blood reduces the need for allogeneic blood transfusion and the aim of the present study was to verify the safety and the clinical efficacy. An observational retrospective study has been conducted on 124 patients, undergoing cemented total knee prosthesis replacement. Observed population was stratified into two g...

  17. The Error in Total Error Reduction

    OpenAIRE

    Witnauer, James E.; Urcelay, Gonzalo P.; Miller, Ralph R.

    2013-01-01

    Most models of human and animal learning assume that learning is proportional to the discrepancy between a delivered outcome and the outcome predicted by all cues present during that trial (i.e., total error across a stimulus compound). This total error reduction (TER) view has been implemented in connectionist and artificial neural network models to describe the conditions under which weights between units change. Electrophysiological work has revealed that the activity of dopamine neurons i...

  18. Total Quality Service and the Business College

    OpenAIRE

    James Perotti

    1995-01-01

    Moving a business college to commit to a total quality service approach is much more difficult than the literature suggests. The commitment to customer satisfaction is the essential focus of total quality service. It is unlikely to occur in business colleges. While small incremental change is readily possible, the values and culture of the faculty and administration prevent the requisite acceptance by the faculty of students as their customers, and acceptance of the faculty as customers of th...

  19. Severe Heterotopic Ossification following Total Knee Replacement

    OpenAIRE

    Dodds, Alexander L.; Keene, Gregory C. R.

    2014-01-01

    Although the incidence of minor heterotopic ossification is probably higher than what is usually expected, severe heterotopic ossification (HO) is an extremely rare event following total knee replacement surgery. We present the case of a 66-year-old woman who initially had achieved an excellent range of motion following bilateral uncemented rotating platform total knee replacement, before presenting with pain and loss of range of motion at 2 months after surgery. Severe HO was diagnosed on X-...

  20. Photoproduction total cross section and shower development

    Science.gov (United States)

    Cornet, F.; García Canal, C. A.; Grau, A.; Pancheri, G.; Sciutto, S. J.

    2015-12-01

    The total photoproduction cross section at ultrahigh energies is obtained using a model based on QCD minijets and soft-gluon resummation and the ansatz that infrared gluons limit the rise of total cross sections. This cross section is introduced into the Monte Carlo system AIRES to simulate extended air showers initiated by cosmic ray photons. The impact of the new photoproduction cross section on common shower observables, especially those related to muon production, is compared with previous results.

  1. Photoproduction total cross section and shower development

    CERN Document Server

    Cornet, F; Grau, A; Pancheri, G; Sciutto, S J

    2015-01-01

    The total photoproduction cross section at ultra-high energies is obtained using a model based on QCD minijets and soft-gluon resummation and the ansatz that infrared gluons limit the rise of total cross sections. This cross section is introduced into the Monte Carlo system AIRES to simulate extended air-showers initiated by cosmic ray photons. The impact of the new photoproduction cross section on common shower observables, especially those related to muon production, is compared with previous results.

  2. Analysis and Accounting of Total Cash Flow

    OpenAIRE

    MELANIA ELENA MICULEAC

    2012-01-01

    In order to reach the objective of supplying some relevant information regarding the liquidity inflows and outflows during a financial exercise, the total cash flow analysis must include the analysis of result cashable from operation, of payments and receipts related to the investment and of financing decisions of the last exercise, as well as the analysis of treasury variation (of cash items). The management of total cash flows ensures the correlation of current liquidness flows as consequen...

  3. Effects of xenobiotics on total antioxidant capacity

    OpenAIRE

    Ferrari, Carlos Kusano Bucalen

    2012-01-01

    The objective of this article was to review the effects of xenobiotics on total antioxidant capacity (TAC). Measurement of TAC is appropriate for evaluation of the total antioxidant defenses of blood, cells, and different kinds of tissues and organs. TAC is reduced by alcoholism, smoking, and exposure to radiation, herbicides, carbon monoxide, carbon tetrachloride, lead, arsenic, mercury, cadmium, aluminum, and other toxic elements. The test is also an important tool in evaluating environment...

  4. Total Ownership Cost -- Tools and Discipline

    OpenAIRE

    Boudreau, Mike; Naegle, Brad

    2011-01-01

    Sponsored Report (for Acquisition Research Program) Control of total ownership cost (TOC) is a continuing initiative to manage costs over the entire life cycle of a weapon system. There are several major categories of costs that contribute to Total Ownership Cost but the principal categories are (1) R&D, (2) Production, (3) Operating and Support, and (4) Disposal. System TOC is the same as Life Cycle Cost (LCC) and must be planned and controlled from requirements definition, system develop...

  5. Management of complications after total shoulder arthroplasty

    OpenAIRE

    Josef K Eichinger; Galvin, Joseph W.

    2015-01-01

    The outcomes of total shoulder arthroplasty (TSA) for painful arthritis of the glenohumeral joint are excellent with significant improvement in pain and function. Increased use of total shoulder arthroplasty over the past decade has led to identification of common complications. Although the complication rate is low, accurate and timely diagnosis, appropriate management, and implementation of methods for prevention are critical to a successful long-term outcome. The most common complications ...

  6. Discrete Total Variation: New Definition and Minimization

    OpenAIRE

    Condat, Laurent

    2016-01-01

    We propose a new definition for the gradient field of a discrete image, defined on a twice finer grid. The differentiation process from the image to its gradient field is viewed as the inverse operation of linear integration, and the proposed mapping is nonlinear. Then, we define the total variation of an image as the l1 norm of its gradient field amplitude. This new definition of the total variation yields sharp edges and has better isotropy than the classical definition.

  7. The Challenge of Total Factor Productivity

    OpenAIRE

    Erwin Diewert

    2000-01-01

    In this article, as part of the symposium on total factor productivity, Erwin Diewert of the University of British Columbia provides a comprehensive discussion of what is needed to develop reliable measures of total factor productivity in terms of output and the different classes of inputs. He concludes that the current system of industry statistics in all advanced countries has not kept up with the evolution of the economy from primary and manufacturing production to the production of servic...

  8. Brauer-Thrall for totally reflexive modules

    CERN Document Server

    Christensen, Lars Winther; Rahmati, Hamidreza; Striuli, Janet; Wiegand, Roger

    2010-01-01

    Let R be a commutative noetherian local ring that is not Gorenstein. It was recently discovered that the category of totally reflexive modules over R is representation infinite, provided that it contains a non-free module. The main goal of this paper is to understand how complex the category of totally reflexive modules can be in this situation. Local rings (R,m) with m^3=0 are commonly regarded as the structurally simplest rings to admit diverse categorical and homological characteristics. For such rings we obtain conclusive results about the category of totally reflexive modules, modeled on the Brauer-Thrall conjectures. Starting from a non-free cyclic totally reflexive module, we construct a family of indecomposable totally reflexive R-modules that contains, for every n in N, a module that is minimally generated by n elements. Moreover, if the residue field R/m is algebraically closed, then we construct for every n in N an infinite family of indecomposable and pairwise non-isomorphic totally reflexive R-mo...

  9. Total lymphoid irradiation and discordant cardiac xenografts

    International Nuclear Information System (INIS)

    Total lymphoid irradiation can prolong concordant cardiac xenografts. The effects of total lymphoid irradiation in a discordant xenograft model (guinea pig to rat) were studied with and without adjuvant pharmacologic immunosuppression. Inbred Lewis rats were randomly allocated to one of four groups. Group 1 (n = 6) served as a control group and rats received no immunosuppression. Group 2 (n = 5) received triple-drug therapy that consisted of intraperitoneal azathioprine (2 mg/kg), cyclosporine (20 mg/kg), and methylprednisolone (1 mg/kg) for 1 week before transplantation. Group 3 animals (n = 5) received 15 Gy of total lymphoid irradiation in 12 divided doses over a 3-week period. Group 4 (n = 6) received both triple-drug therapy and total lymphoid irradiation as described for groups 2 and 3. Complement-dependent cytotoxicity assay was performed to determine if a correlation between complement-dependent cytotoxicity and rejection-free interval existed. Rejection was defined as cessation of graft pulsation and was confirmed by histologic test results. Only groups 1 and 2 showed a difference in survival (group 1, 6.9 +/- 1.0 minutes; group 2, 14.2 +/- 2.7 minutes, p = 0.02). Although total lymphoid irradiation did decrease complement-dependent cytotoxicity, linear regression revealed no correlation between complement-dependent cytotoxicity and graft survival (coefficient of correlation, 0.30). Unlike concordant cardiac xenografts, total lymphoid irradiation with or without triple-drug therapy does not prolong graft survival

  10. Total lymphoid irradiation and discordant cardiac xenografts

    Energy Technology Data Exchange (ETDEWEB)

    Kaplan, E.; Dresdale, A.R.; Diehl, J.T.; Katzen, N.A.; Aronovitz, M.J.; Konstam, M.A.; Payne, D.D.; Cleveland, R.J. (Tufts Univ. School of Medicine, Boston, MA (USA))

    1990-01-01

    Total lymphoid irradiation can prolong concordant cardiac xenografts. The effects of total lymphoid irradiation in a discordant xenograft model (guinea pig to rat) were studied with and without adjuvant pharmacologic immunosuppression. Inbred Lewis rats were randomly allocated to one of four groups. Group 1 (n = 6) served as a control group and rats received no immunosuppression. Group 2 (n = 5) received triple-drug therapy that consisted of intraperitoneal azathioprine (2 mg/kg), cyclosporine (20 mg/kg), and methylprednisolone (1 mg/kg) for 1 week before transplantation. Group 3 animals (n = 5) received 15 Gy of total lymphoid irradiation in 12 divided doses over a 3-week period. Group 4 (n = 6) received both triple-drug therapy and total lymphoid irradiation as described for groups 2 and 3. Complement-dependent cytotoxicity assay was performed to determine if a correlation between complement-dependent cytotoxicity and rejection-free interval existed. Rejection was defined as cessation of graft pulsation and was confirmed by histologic test results. Only groups 1 and 2 showed a difference in survival (group 1, 6.9 +/- 1.0 minutes; group 2, 14.2 +/- 2.7 minutes, p = 0.02). Although total lymphoid irradiation did decrease complement-dependent cytotoxicity, linear regression revealed no correlation between complement-dependent cytotoxicity and graft survival (coefficient of correlation, 0.30). Unlike concordant cardiac xenografts, total lymphoid irradiation with or without triple-drug therapy does not prolong graft survival.

  11. 38 CFR 3.340 - Total and permanent total ratings and unemployability.

    Science.gov (United States)

    2010-07-01

    ... impairment of mind or body which is sufficient to render it impossible for the average person to follow a... Evaluations; Service Connection § 3.340 Total and permanent total ratings and unemployability. (a)...

  12. Cataract incidence after total-body irradiation

    International Nuclear Information System (INIS)

    Purpose: Aim of this retrospective study was to evaluate cataract incidence in a homogeneous group of patients after total-body irradiation followed by autologous bone marrow transplantation or peripheral blood stem cell transplantation. Method and Materials: Between 11/1982 and 6/1994 in total 260 patients received in our hospital total-body irradiation for treatment of haematological malignancy. In 1996-96 patients out of these 260 patients were still alive. 85 from these still living patients (52 men, 33 women) answered evaluable on a questionnaire and could be examined ophthalmologically. Median age of these patients was 38,5 years (15 - 59 years) at time of total-body irradiation. Radiotherapy was applied as hyperfractionated total-body irradiation with a median dose of 14,4 Gy in 12 fractions over 4 days. Minimum time between fractions was 4 hours, photons with a energy of 23 MeV were used, and the dose rate was 7 - 18 cGy/min. Results: Median follow-up is now 5,8 years (1,7 - 13 years). Cataract occurred in (28(85)) patients after a median time of 47 months (1 - 104 months). In 6 out of these 28 patients who developed a cataract, surgery of the cataract was performed. Whole-brain irradiation prior to total-body irradiation was more often in the group of patients developing a cataract (14,3%) vs. 10,7% in the group of patients without cataract. Conclusion: Cataract is a common side effect of total-body irradiation. Cataract incidence found in our patients is comparable to results of other centres using a fractionated regimen for total-body irradiation. The hyperfractionated regimen used in our hospital does obviously not result in a even lower cataract incidence. In contrast to acute and late toxicity in other organ/organsystems, hyperfractionation of total-body irradiation does not further reduce toxicity for the eye-lens. Dose rate may have more influence on cataract incidence

  13. Total lymphoid irradiation of intractable rheumatoid arthritis

    International Nuclear Information System (INIS)

    Eleven patients with intractable rheumatoid arthritis were treated with fractionated total lymphoid irradiation, (total dose 20 Gy). Lasting improvement in clinical symptoms was found in four patients during treatment and the remaining patients experienced similar benefit within 2 months of irradiation. There was marked reduction in exacerbations and number of joints involved. Morning stiffness, joint swelling and tenderness decreased. Complications included severe fatigue during treatment and acute bacterial arthritis in multiple joints in one patient. Four patients have since died, one of renal failure, another of cardiogenic shock following surgery 3 and 24 months after total lymphoid irradiation. Both had generalised amyloidosis. The third patient developed joint empyema and died of toxic cardiac failure. The fourth died 3 months after resection of a Kaposi's sarcoma complicated by wound infection which responded to treatment. Immunologically, total lymphoid irradiation resulted in suppression of the absolute lymphocyte count and reduction in T-helper cells, the number of T-suppressor cells remaining unchanged. These data provide evidence of T-cell involvement in the pathogenesis of rheumatoid arthritis. Total lymphoid irradiation can induce sustained improvement in clinical disease activity, but severe, possibly fatal, side-effects cannot be ignored. (author)

  14. Current status of permanent total artificial hearts.

    Science.gov (United States)

    Davis, P K; Rosenberg, G; Snyder, A J; Pierce, W S

    1989-01-01

    Pneumatic total artificial heats, although demonstrating utility as temporary mechanical circulatory support devices, have not demonstrated a great deal of promise as permanent cardiac replacements. The increasing number of patients who would be candidates for total heart replacement suggests a large role for a permanent implantable total artificial heart. To that end, the Pennsylvania State University is developing an electric motor-driven total artificial heart; the results with implants in calves are encouraging. In this device, a roller-screw mechanism is used to translate the rotation of a brushless direct-current motor into rectilinear motion of a pusher-plate assembly, which in turn empties the blood sacs. The total artificial heart of the future will function under automatic control without percutaneous leads, and this should provide the patient with a nearly normal life-style. Although further experimental efforts are necessary to prepare the device for clinical trials, the technology to provide a safe and reliable electric blood-pump system is at hand. PMID:2912392

  15. Assay development status report for total cyanide

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, B.C. [Westinghouse Hanford Co., Richland, WA (United States); Jones, T.E.; Pool, K.H. [Pacific Northwest Lab., Richland, WA (United States)

    1993-02-01

    A validated cyanide assay that is applicable to a variety of tank waste matrices is necessary to resolve certain waste tank safety issues and for purposes of overall waste characterization. The target for this effort is an assay with an applicable range of greater than 1,000 ppM (0.10 wt%) total cyanide and a confidence level greater than 80%. Figure 1 illustrates the operating regime of the proposed cyanide assay method. The Assay Development Status Report for Total Cyanide will summarize the past experience with cyanide analyses on-tank waste matrices and will rate the status of the analytical methods used to assay total cyanide (CN{sup {minus}} ion) in the tank waste matrices as acceptable or unacceptable. This paper will also briefly describe the current efforts for improving analytical resolution of the assays and the attempts at speciation.

  16. Severe Heterotopic Ossification following Total Knee Replacement

    Directory of Open Access Journals (Sweden)

    Alexander L. Dodds

    2014-01-01

    Full Text Available Although the incidence of minor heterotopic ossification is probably higher than what is usually expected, severe heterotopic ossification (HO is an extremely rare event following total knee replacement surgery. We present the case of a 66-year-old woman who initially had achieved an excellent range of motion following bilateral uncemented rotating platform total knee replacement, before presenting with pain and loss of range of motion at 2 months after surgery. Severe HO was diagnosed on X-rays. Treatment consisted of nonoperative measures only, including physiotherapy with hydrotherapy and anti-inflammatories. She eventually regained her range of motion when seen at 8 months after operation. This case illustrates that nonoperative treatment without the use of radiotherapy or surgery can be used to safely resolve stiffness caused by HO after total knee replacement.

  17. Heterotopic bone formation following total shoulder arthroplasty

    DEFF Research Database (Denmark)

    Kjaersgaard-Andersen, P.; Frich, Lars Henrik; Sjøbjerg, J.O.;

    1989-01-01

    the glenohumeral and/or the glenoacromial space. There was no correlation between shoulder pain and the development of ossification. Shoulders with grade III heterotopic bone formation had a limited range of active elevation compared with shoulders without or with only a milder lesion. Men and......The incidence and location of heterotopic bone formation following total shoulder arthroplasty were evaluated in 58 Neer Mark-II total shoulder replacements. One year after surgery, 45% had developed some ectopic ossification. In six shoulders (10%) the ossifications roentgenographically bridged...... patients with osteoarthritis of the shoulder joint were significantly disposed to the development of heterotopic bone. Heterotopic bone formation following total shoulder arthroplasty is frequent, but disabling heterotopic ossifications seem to be rare....

  18. Total reflection X-ray fluorescence analysis

    International Nuclear Information System (INIS)

    In the past few years, total reflection X-ray flourescence analysis (TXRF) has found an increasing number of assignments and applications. Experience of trace element analysis using TXRF and examples of applications are already widespread. Therefore, users of TXRF had the opportunity of an intensive exchange of their experience at the 1st workshop on total reflection X-ray fluorescence analysis which took place on May 27th and 28th 1986 at the GKSS Research Centre at Geesthacht. In a series of lectures and discussions dealing with the analytical principle itself, sample preparation techniques and applications as well as comuter programs for spectrum evaluation, the present state of development and the range of applications were outlined. 3 studies out of a total of 14 were included separately in the INIS and ENERGY databases. With 61 figs., 12 tabs

  19. Total quality management in orthodontic practice.

    Science.gov (United States)

    Atta, A E

    1999-12-01

    Quality is the buzz word for the new Millennium. Patients demand it, and we must serve it. Yet one must identify it. Quality is not imaging or public relations; it is a business process. This short article presents quality as a balance of three critical notions: core clinical competence, perceived values that our patients seek and want, and the cost of quality. Customer satisfaction is a variable that must be identified for each practice. In my practice, patients perceive quality as communication and time, be it treatment or waiting time. Time is a value and cost that must be managed effectively. Total quality management is a business function; it involves diagnosis, design, implementation, and measurement of the process, the people, and the service. Kazien is a function that reduces value services, eliminates waste, and manages time and cost in the process. Total quality management is a total commitment for continuous improvement. PMID:10587600

  20. Total artificial hearts: past, present, and future.

    Science.gov (United States)

    Cohn, William E; Timms, Daniel L; Frazier, O H

    2015-10-01

    A practical artificial heart has been sought for >50 years. An increasing number of people succumb to heart disease each year, but the number of hearts available for transplantation remains small. Early total artificial hearts mimicked the pumping action of the native heart. These positive-displacement pumps could provide adequate haemodynamic support and maintain the human circulation for short periods, but large size and limited durability adversely affected recipients' quality of life. Subsequent research into left ventricular assist devices led to the use of continuous-flow blood pumps with rotating impellers. Researchers have attempted to integrate this technology into modern total artificial hearts with moderate clinical success. The importance of pulsatile circulation remains unclear. Future research is, therefore, needed into positive-displacement and rotary total artificial hearts. PMID:26031698

  1. Total quantum Zeno effect beyond Zeno time

    International Nuclear Information System (INIS)

    In this work we show that is possible to obtain Total Quantum Zeno Effect in an ustable systems for times larger than the correlation time of the bath. The effect is observed for some particular systems in which one can chose appropriate observables which frequent measurements freeze the system into the initial state. For a two level system in a squeezed bath one can show that there are two bath dependent observables displaying Total Zeno Effect when the system is initialized in some particular states. We show also that these states are intelligent states of two conjugate observables associated to the electromagnetic fluctuations of the bath

  2. TOTAL FINA ELF. Annual report 2002

    International Nuclear Information System (INIS)

    This document is the annual report 2002 of Total-Fina-Elf society, great company on the hydrocarbons market. According to the company objective (set the standard not only with the financial performance, but also with stringent requirements in terms of social and environmental responsibility), it presents the Chairman message, the corporate governance, the social and environmental responsibility, the future of energy, the human resources policy, the investor relations, the overview of Total-Fina-Elf fiscal year with financial information and 2002 industrial events. (A.L.B.)

  3. ANALYSIS AND ACCOUNTING OF TOTAL CASH FLOW

    Directory of Open Access Journals (Sweden)

    MELANIA ELENA MICULEAC

    2012-01-01

    Full Text Available In order to reach the objective of supplying some relevant information regarding the liquidity inflows and outflows during a financial exercise, the total cash flow analysis must include the analysis of result cashable from operation, of payments and receipts related to the investment and of financing decisions of the last exercise, as well as the analysis of treasury variation (of cash items. The management of total cash flows ensures the correlation of current liquidness flows as consequence of receipts with the payments ’flows, in order to provide payment continuity of mature obligations.

  4. Distant set distinguishing total colourings of graphs

    OpenAIRE

    Przybyło, Jakub

    2015-01-01

    The Total Colouring Conjecture suggests that $\\Delta+3$ colours ought to suffice in order to provide a proper total colouring of every graph $G$ with maximum degree $\\Delta$. Thus far this has been confirmed up to an additive constant factor, and the same holds even if one additionally requires every pair of neighbours in $G$ to differ with respect to the sets of their incident colours, so called pallets. Within this paper we conjecture that an upper bound of the form $\\Delta+const.$ still re...

  5. Total synthesis of palau'amine

    OpenAIRE

    Namba, Kosuke; Takeuchi, Kohei; Kaihara, Yukari; Oda, Masataka; Nakayama, Akira; Nakayama, Atsushi; YOSHIDA, Masahiro; Tanino, Keiji

    2015-01-01

    Palau'amine has received a great deal of attention in the past two decades as an attractive synthetic target by virtue of its intriguing molecular architecture and significant immunosuppressive activity. Here we report the total synthesis of palau'amine characterized by the construction of an ABDE tetracyclic ring core including a trans-bicylo[3.3.0]octane skeleton at a middle stage of total synthesis. The ABDE tetracyclic ring core is constructed by a cascade reaction of a cleavage of the N–...

  6. TOTAL 2003 activities report in brief

    International Nuclear Information System (INIS)

    This activities report presents the activities of the petroleum industry Group Total for the year 2003. The following topics are detailed: the corporate social responsibility with the environment stewardship, the energy future management, the safety enhancing, the human resources and the ethics and local development; the shareholder information with the Total share and the share-holding structure; the activities with informations on the Group, the main events, the upstream exploration and production,, the downstream refining, marketing, trading and shipping, the chemicals with overview 2003, base chemical and polymers, performance and specialities. (A.L.B.)

  7. Systematic Calculations of Total Atomic Binding Energies

    International Nuclear Information System (INIS)

    We have calculated total atomic binding energies of 3- to 91-electron ions of all atoms with Z=3 to 118, in the Dirac-Fock model, for applications to atomic mass determination from highly-charged ions. In this process we have determined the ground-state configuration of many ions for which it was not known. We also provide total electronic correlation including Breit correlation for iso-electronic series of beryllium, neon, magnesium and argon, using the multiconfiguration Dirac-Fock approach.

  8. Total Mercury in Lake Neusiedl, Austria

    OpenAIRE

    Jirsa F.; Pirker D.; Krachler R.

    2013-01-01

    Between May and September 2011 a total of 361 samples from water, sediment, macrophytes and fish tissues from the shallow, slightly alkaline Lake Neusiedl were measured for their total mercury content with cold vapour atomic absorption spectroscopy (CV-AAS). Hg content of surface water was below the LOD of 0.1 μg/L and the sediments displayed contents between 0.025 and 0.113 μg/g dw, significantly correlated with the proportion of organic components (fig 1). Although these results do not poin...

  9. Total positive curvature of circular DNA

    DEFF Research Database (Denmark)

    Bohr, Jakob; Olsen, Kasper Wibeck

    2013-01-01

    micro-DNAs longer than the minimum length must be concave, a result that is consistent with typical atomic force microscopy images of plasmids. Predictions for the total positive curvature of circular micro-DNAs are given as a function of length, and comparisons with circular DNAs from the literature...... molecules, e.g., plasmids, it is shown to have implications for the total positive curvature integral. For small circular micro-DNAs it follows as a consequence of Fenchel's inequality that there must exist a minimum length for the circular plasmids to be double stranded. It also follows that all circular...

  10. PRIVATE EQUITY INVESTING AND TOTAL QUALITY - UPDATED

    Directory of Open Access Journals (Sweden)

    Nikola Stefanovic

    2013-03-01

    Full Text Available Private equity funds invest money into companies and, in return, receive stakes in the companies' equity, thus becoming the partners who share the business risk. Because of that, private equity funds increase the value of their portfolio companies, by, among other things, improving their internal processes and strengthening their market positions. While doing that, private equity funds place a special emphasis on the implementation of the total quality. In order to do that, they focus on the three key elements for the successful implementation of the total quality: strategy-based organization, focus on consumers, and obsession with quality.

  11. TECAB - Totally Endoscopic Coronary Artery Bypass

    Medline Plus

    Full Text Available ... completely endoscopic coronary artery bypass grafting procedure using robotics. We call this operation a “TECAB,” “Totally Endoscopic ... scrub nurse, also a lot of experience with robotics now. And Dr. Atiq Rahman, fellow here for ...

  12. Total synthesis of insect antifeedant drimane sesquiterpenes.

    NARCIS (Netherlands)

    Jansen, B.J.M.

    1993-01-01

    The investigations described in this thesis deal with the total synthesis of sesquiterpenes of the drimane family, named for their widespread occurrence in the stem bark of South American Drimys species. These compounds contain the bicyclofarnesol nucleus 1 , which is invariably oxi

  13. Herpes zoster ophthalmicus with total ophthalmoplegia

    Directory of Open Access Journals (Sweden)

    Talwar S

    1990-01-01

    Full Text Available A case of unilateral herpes zoster ophthalmicus (HZO is reported with ipsilateral involvement of III, IV and VI cranial nerves which led to extra ocular muscles palsy presenting as total ophthalmopegia along with ptosis, cycloplegia and dilated non reactive pupil.

  14. Dilemmas in Uncemented Total Hip Arthroplasty

    NARCIS (Netherlands)

    Goosen, J.H.M.

    2009-01-01

    In this thesis, different aspects that are related to the survivorship and clinical outcome in uncemented total hip arthroplasty are analysed. In Chapter 2, the survival rate, Harris Hip score and radiographic features of a proximally hydroxyapatite coated titanium alloy femoral stem (Bi-Metric, Bio

  15. TECAB - Totally Endoscopic Coronary Artery Bypass

    Medline Plus

    Full Text Available ... common cardiac problem. The abbreviation we as doctors use for this operation is “TECAB,” meaning “Totally Endoscopic ... point. It’s down. It’s down already. So we use a double-lumen tube. We have those Weitlander. ...

  16. Radiological findings in total colonic aganglionosis

    International Nuclear Information System (INIS)

    The radiological findings pathognomonic of Hirschsprung's disease have been known for quite a long time. However, in addition to those diseases characterized by rectum or rectum-sigmoid aganglionosis (as in the classic form of Hirschsprung's disease), in pediatric pathology of surgical interest severe affections exist characterized by aganglionosis extending from the rectum to the entire colon, and exceptionally as far as the small bowel (ultra-long Hirschsprung's disease). The authors report on the results they obtained in radiological studies of 6 cases of total colonic aganglionosis by means of the current radiological procedures, i.e. plain abdominal films and barium enema. As for total colonic aganglionosis, no diagnostic radiological parameters have been assessed yet. The authors compare their results with those taken from international literature: microcolon with reflux into megaileum (2 out of 6 cases) appears to be the most suggestive X-ray finding for total colonic aganglionosis. Finally, the role is discussed of radiological studies in the diagnostic approach to total colonic aganglionosis. The authors conclude that, even though radiological investigations are indispensable, they are often not conclusive. Therefore, an accurate evaluation of the proximal extension of aganglionosis can be made only at surgery

  17. Stereocontrolled total synthesis of hedyotol A.

    Science.gov (United States)

    Kawabe, Yusuke; Ishikawa, Ryo; Akao, Yusuke; Yoshida, Atsushi; Inai, Makoto; Asakawa, Tomohiro; Hamashima, Yoshitaka; Kan, Toshiyuki

    2014-04-01

    The total synthesis of hedyotol A (1), a natural product isolated from Hedyotis lawsoniae (DC.) Wight et Arn. (Rubiaceae), was accomplished in a highly stereocontrolled manner. Key steps include an L-proline-catalyzed cross-aldol reaction and the biomimetic construction of a furofuran lignan skeleton through a quinomethide intermediate. PMID:24660822

  18. Production Function Geometry with "Knightian" Total Product

    Science.gov (United States)

    Truett, Dale B.; Truett, Lila J.

    2007-01-01

    Authors of principles and price theory textbooks generally illustrate short-run production using a total product curve that displays first increasing and then diminishing marginal returns to employment of the variable input(s). Although it seems reasonable that a temporary range of increasing returns to variable inputs will likely occur as…

  19. The total synthesis of (–)-crispatene

    OpenAIRE

    Miller, Aubry K.; Byun, Daniel H.; Beaudry, Christopher M.; Trauner, Dirk

    2004-01-01

    The total synthesis of the molluscan polypropionate (–)-crispatene is described. The synthesis features a palladium-catalyzed cross-coupling to establish a sensitive conjugated tetraene and its Lewis acid-catalyzed cycloisomerization to yield the bicyclo[3.1.0]hexene core of the natural product. The absolute configuration of (–)-crispatene and related molecules is established.

  20. Enantioselective Total Synthesis of (+)-Salvileucalin B

    OpenAIRE

    Levin, Sergiy; Nani, Roger R.; Reisman, Sarah E.

    2011-01-01

    An enantioselective total synthesis of the diterpenoid natural product (+)-salvileucalin B is reported. Key findings include a copper-catalyzed arene cyclopropanation reaction to provide the unusual norcaradiene core and a reversible retro-Claisen rearrangement of a highly functionalized norcaradiene intermediate.

  1. Revision Total Hip Replacement: A Case Report

    Directory of Open Access Journals (Sweden)

    Md Hafizur Rahman

    2013-07-01

    Full Text Available Total hip replacement is a reconstructive procedure that has improved the management of those diseases of the hip joint that have responded poorly to conventional medical therapy. Conventional, primary total hip replacement is a durable operation in the majority of patients. A hip replacement is a mechanical device with parts that are assembled before and during the operation. But the possible complications of total hip arthroplasty, and its clinical performance over time, is a challenging occasion to the surgeons, and such a challenge we faced with our presenting patient. A 68 year old lady with history of cemented bipolar hemiarthroplasty done in a tertiary care hospital, due to fracture neck of the left femur having the history of diabetes, chronic kidney disease, heart disease, anaemia, and mental disorders presented with loosened prosthesis, thinning of medial proximal cortex of the femur which had broken within few months after surgery. She complained of painful walking at left hip joint. There was also evidence of chronic infective and degenerative arthritis of acetabular component of the affected hip joint. Cemented revision total hip replacement surgery was performed with expert multidisciplinary involvement. On 2nd postoperative day the patient was allowed to walk on operated limb with the aid of walker. On 12th postoperative day all the stitches were removed and wound was found healthy.

  2. Total Quality Management. ERIC Digest, Number 73.

    Science.gov (United States)

    Weaver, Tyler

    The Japanese success story has made W. Edwards Deming's Total Quality Management (TQM) theory increasingly popular among American managers, from car manufacturers to educational leaders. TQM is based on two tenets: the primacy of customer satisfaction and the necessity of tapping nontraditional sources (especially employee ideas) to institute…

  3. A review of total body irradiation

    International Nuclear Information System (INIS)

    This review of total body irradiation discusses the optimization of the prescription, relevant radiobiological research, cytotoxic drugs and TBI, and the delivery of TBI and its complications, with particular reference to acute effects, neurological sequelae, endocrine effects, cataracts, and secondary malignancies. (U.K.)

  4. Total pressing Indonesian gas development, exports

    International Nuclear Information System (INIS)

    Total is on track to become Indonesia's leading gas exporter by the turn of the century. Total's aggressive development of its Mahakam Delta acreage in East Kalimantan is intended to keep pace with growing liquefied natural gas demand, mainly from Japan but also increasingly from South Korea and Taiwan. A frantic scramble is under way among natural gas suppliers in the Pacific Rim region, particularly those with current LNG export facilities, to accommodate projections of soaring natural gas demand in the region. Accordingly, Total's Indonesian gas production goal is the centerpiece of a larger strategy to become a major player in the Far East Asia gas scene. Its goals also fall in line with Indonesia's. Facing flat or declining oil production while domestic oil demand continues to soar along with a rapidly growing economy, Indonesia is heeding some studies that project the country could become a net oil importer by the turn of the century. The paper describes Total's Far East strategy, the Mahakam acreage which it operates, the shift to gas development, added discoveries, future development, project spending levels, and LNG export capacity

  5. Total Synthesis of (-)-Nemorosone and (+)-Secohyperforin.

    Science.gov (United States)

    Sparling, Brian A; Tucker, James K; Moebius, David C; Shair, Matthew D

    2015-07-17

    A general strategy for the synthesis of polycyclic polyprenylated acylphloroglucinols is described in which a scalable, Lewis acid catalyzed epoxide-opening cascade cyclization is used to furnish common intermediate 4. The utility of this approach is exemplified by the total syntheses of both ent-nemorosone and (+)-secohyperforin, which were each accomplished in four steps from this intermediate. PMID:26125288

  6. Total Synthesis of balanol, Part 2

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Kelly, Nicholas; Tedenborg, Lars;

    1997-01-01

    A convergent enantioselective total synthesis of the natural product (-)-balanol (1) is described. In addition to benzophenone fragment 8, key intermediates are chiral bicyclic aziridine 3 and the corresponding epoxide 4, both of which undergo highly regio- and stereoselective nucleophilic ring...

  7. Enantioselective Total Synthesis of Plectosphaeroic Acid B

    OpenAIRE

    Jabri, Salman Y.; Overman, Larry E.

    2013-01-01

    The first total synthesis of a member of the plectosphaeroic acid family of fungal natural products is reported. Key steps include the late-stage formation of the hindered N6–C9″ bond and stereoselective introduction of the two methylthio substituents.

  8. Transanal total mesorectal excision - a systematic review

    DEFF Research Database (Denmark)

    Bjørn, Maya Xania; Perdawood, Sharaf Karim

    2015-01-01

    dissection. We aimed to evaluate the literature on TaTME. METHODS: We performed a systematic search of the literature in the PubMed and Embase databases. Both authors assessed the studies. All publications on TaTME were included with the exception of review articles. RESULTS: A total of 29 studies (336...

  9. Periprosthetic osteolysis after total wrist arthroplasty

    DEFF Research Database (Denmark)

    Boeckstyns, Michel E H; Herzberg, Guillaume

    2014-01-01

    Background and Literature Review Periprosthetic osteolysis (PPO) after second- or third-generation total wrist arthroplasty (TWA), with or without evident loosening of the implant components, has previously been reported in the literature, but rarely in a systematic way. Purpose The purpose of th...

  10. Application of Total Quality Management in Education

    Science.gov (United States)

    Farooq, M. S.; Akhtar, M. S.; Ullah, S. Zia; Memon, R. A.

    2007-01-01

    The purpose of the paper is to analyzing thoughts of the modern management paradigm "Total Quality Management" (TQM), and its application in the field of education. The basic theme of TQM is participatory approach to address the question(s) of quality in business aswell as in the field of education. Reviewing fresh literature from the internet …

  11. An approach to total quality assurance

    International Nuclear Information System (INIS)

    Total Quality Assurance must be based on amalgamating three quality functions: effective quality control, competent inspection, and regularly audited Quality Assurance programmes. In applying these functions the fuel supplier must regard each of his sub-contractors as part of his own works and ensure a common policy of motivated Quality Assurance throughout his own works and those of his suppliers. (author)

  12. [Open total dislocation of the talus].

    Science.gov (United States)

    Grabski, R S; Sosiński, R

    1992-01-01

    A case of 35 years old patient with open, total, fixed dislocation of the talus reduced with heel traction is presented. The Sudeck syndrome subsided after one year. Weight bearing was not allowed for 7 months. An examination after 2.5 years revealed minor osteoarthritis, full range of movement in the foot but limited walking capability. PMID:7555299

  13. A modified total synthesis of cystothiazole A

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A modified total synthesis of cystothiazole A is described. In this synthetic strategy, a one-step transformation of acylated oxazolidinone to β-ketoester has been successfully applied, thus making the synthetic route more efficient. This method may also be potentially applied in synthesis of other related β-substituted-β-methoxyl acrylates (bb-MOAs).

  14. Total Quality Management in Higher Education.

    Science.gov (United States)

    Sherr, Lawrence A.; Lozier, G. Gredgory

    1991-01-01

    Total Quality Management, based on theories of W. Edward Deming and others, is a style of management using continuous process improvement characterized by mission and customer focus, a systematic approach to operations, vigorous development of human resources, long-term thinking, and a commitment to ensuring quality. The values espoused by this…

  15. Total internal reflection laser tools and methods

    Energy Technology Data Exchange (ETDEWEB)

    Zediker, Mark S.; Faircloth, Brian O.; Kolachalam, Sharath K.; Grubb, Daryl L.

    2016-02-02

    There is provided high power laser tools and laser heads that utilize total internal reflection ("TIR") structures to direct the laser beam along a laser beam path within the TIR structure. The TIR structures may be a TIR prism having its hypotenuse as a TIR surface.

  16. Riemann surfaces and totally real tori

    OpenAIRE

    Duval, Julien; Gayet, Damien

    2009-01-01

    Given a generic totally real torus unknotted in the unit sphere of the complex plane, we prove the following alternative : either there exists a filling of the torus by holomorphic discs and the torus is rationally convex, or its rational hull contains a holomorphic annulus.

  17. Total Knee Replacement (Arthroplasty) (Beyond the Basics)

    Science.gov (United States)

    ... demonstrate that 80 to 90 percent of total knees will last between 15 to 20 years, early failures may occur due to a variety of reasons. These include loosening of the implants, infection, fractures of the bone around the implants, and instability. ...

  18. Total synthesis of (S)-equol.

    Science.gov (United States)

    Heemstra, Jennifer M; Kerrigan, Sean A; Doerge, Daniel R; Helferich, William G; Boulanger, William A

    2006-11-23

    The first enantioselective total synthesis of (S)-equol is reported. The described route relies on an Evans alkylation to form the stereocenter and an intramolecular Buchwald etherification to generate the chroman ring. Key features of this method include its brevity, its scalability, and the low cost of starting materials. [reaction: see text]. PMID:17107042

  19. Brutally Unfair Tactics Totally OK Now

    DEFF Research Database (Denmark)

    Wilson, Douglas

    2011-01-01

    In this paper, I use a party game that I co-designed, Brutally Unfair Tactics Totally OK Now (B.U.T.T.O.N.), as a case study to suggest some alternative possibilities for the design of digitally-mediated play and games. Specifically, I argue that that intentionally “broken” or otherwise incomplet...

  20. Capital gains, total returns and saving rates

    OpenAIRE

    Michael Hudson

    2013-01-01

    To focus on the dynamics of how financial wealth is created, obtained, and valued, this paper (1) distinguishes capital gains from income by measuring total returns, and (2) contrasts the capitalized value of rentier income (rent extraction rights and privileges from land, natural resources, and monopolies) from that of industrial profits on tangible capital investment.

  1. The total synthesis of pantocin B.

    Science.gov (United States)

    Sutton, A E; Clardy, J

    2000-02-10

    [reaction: see text] Pantocin B, an unusual antibiotic produced by Erwinia herbicola, effectively controls E. amylovora, the pathogen causing the plant disease fire blight. A total synthesis of pantocin B from L-alanine, glycine, and L-malic acid is reported. PMID:10814312

  2. The total synthesis of (-)-cryptocaryol A.

    Science.gov (United States)

    Dias, L C; Kuroishi, P K; de Lucca, E C

    2015-03-28

    A stereoselective total synthesis of (-)-cryptocaryol A (1) is described. Key features of the 17-step route include the use of three boron-mediated aldol reaction-reduction sequences to control all stereocenters and an Ando modification of the Horner-Wadsworth-Emmons olefination that permitted the installation of the Z double bond of the α-pyrone ring. PMID:25695350

  3. Concepts of total quality management in radiology

    International Nuclear Information System (INIS)

    Quality is one of the touch-stones to determine the competitive advantage for a service, product or company. Total Quality Management has a large ambit, which encompasses not only the quality of images and services producing these images, but also the customers satisfaction. In health care patients satisfaction is divided into three parts: patient quality, professional quality and management quality

  4. TECAB - Totally Endoscopic Coronary Artery Bypass

    Medline Plus

    Full Text Available ... as doctors use for this operation is “TECAB,” meaning “Totally Endoscopic Coronary Artery Bypass.” This procedure will ... make sure his vessels are able for bypass, meaning doing the CT angiograph for the peripheral arteries. ...

  5. Isolation of total RNA from pollens.

    Science.gov (United States)

    Bijli, K M; Singh, B P; Sridhara, S; Arora, N

    2001-05-01

    Isolation of total RNA from plant materials has been difficult, due to the presence of complex organic substances and the associated pigmentation. In fact, there is a dearth of standardized protocols for isolating total RNA from pollens. To find a simple and reliable method for isolating total RNA from pollen, four methods, viz. phenol/SDS (PS), guanidine HCl (GH), tri-reagent (TR), and modified SDS-betaME (SB) were tested with fresh pollen of Ricinus communis (procured at -70 degrees C) and pollen dried at 30-37 degrees C. The quality and quantity of RNA was superior for the material processed at -70 degrees C. SB gave the highest RNA yield (2.35 mg/g, OD260/280 >2.0), compared to other methods. The results obtained by the SB method were found to be comparable with the widely used tri-reagent method. This was validated with other pollens of Imperata cylindrica and Xanthium strumarium. The yield obtained from graded amounts of pollen was consistent with SB, compared to the TR method. The RNA isolated by SB gave good quality mRNA for synthesizing cDNA. The SDS-betaME method is simple, efficient, and uses less expensive reagents. Hence, we recommend the modified SDS-betaME method for isolating total RNA from pollens. PMID:11426703

  6. TECAB - Totally Endoscopic Coronary Artery Bypass

    Medline Plus

    Full Text Available ... coronary artery bypass grafting procedure using robotics. We call this operation a “TECAB,” “Totally Endoscopic Coronary Artery ... see 2 the heart beating behind what we call the “pericardium,” the sack where the heart is ...

  7. Revitalizing Space Operations through Total Quality Management

    Science.gov (United States)

    Baylis, William T.

    1995-01-01

    The purpose of this paper is to show the reader what total quality management (TQM) is and how to apply TQM in the space systems and management arena. TQM is easily understood, can be implemented in any type of business organization, and works.

  8. Diagnosing total quality management - Part 1

    NARCIS (Netherlands)

    Bossink, B.A.G.; Gieskes, J.F.B.; Pas, T.N.M.

    1992-01-01

    From extensive literature research a total quality management (TQM) model is developed. This model describes the basic elements of the concept of TQM. It also provides the way in which the basic elements can be made operational in practice. Based on this model a quality-diagnostical instrument is de

  9. Diagnosing total quality management - Part 2

    NARCIS (Netherlands)

    Bossink, B.A.G.; Gieskes, J.F.B.; Pas, T.N.M.

    1993-01-01

    From extensive literature research a total quality management (TQM) model is developed. This model describes the basic elements of the concept of TQM. It also provides the way in which the basic elements can be made operational in practice. Based on this model a quality-diagnostical instrument is de

  10. Coordinating Council. Ninth Meeting: Total Quality Management

    Science.gov (United States)

    1992-01-01

    This report summarizes the 9th meeting of the STI Coordinating Council. The council listened to the speakers' understanding of Total Quality Management (TQM) principles and heard stories of successful applications of these principles. Definitions of quality stated were focused on customer satisfaction. Reports presented by the speakers are also included.

  11. Total dislodgement of the femoral component following cemented total knee arthroplasty: a case report

    OpenAIRE

    Arac, Sukru; Karatosun, Vasfi

    2004-01-01

    Total dislodgement of the components, which is the most severe form of loosening, has hitherto been unreported following total knee arthroplasty. An eighty-four-year-old woman presented with complaints of pain and sensation of insecurity of her right knee after cemented total knee arthroplasty. On physical examination, a clunk was elicited during movements of the knee; however, radiographs appeared normal except for a separated fragment of the medial femoral condyle. Further examination with ...

  12. Overhead Concentration Platform of Total Withdrawal Operation in Cyclic Total Reflux Batch Distillation

    Institute of Scientific and Technical Information of China (English)

    JIANG Zhankun; BAI Peng

    2011-01-01

    The total withdrawal operation is an inevitable section in cyclic total reflux batch distillation.In the operation,an interesting phenomenon "overhead concentration platform"(OCP) appears,which is defined as a period of time with high overhead concentrations when the operation is changed from total reflux to total withdrawal.The OCP phenomenon and its influential factors,such as the theoretical stage number,feed concentration,and feed composition,are examined by simulations and experiments.The experimental equipment is a column with random packings.It is shown that the number of theoretical stages influences the OCP more significantly than the other factors.

  13. Increasing productivity through Total Reuse Management (TRM)

    Science.gov (United States)

    Schuler, M. P.

    1991-01-01

    Total Reuse Management (TRM) is a new concept currently being promoted by the NASA Langley Software Engineering and Ada Lab (SEAL). It uses concepts similar to those promoted in Total Quality Management (TQM). Both technical and management personnel are continually encouraged to think in terms of reuse. Reuse is not something that is aimed for after a product is completed, but rather it is built into the product from inception through development. Lowering software development costs, reducing risk, and increasing code reliability are the more prominent goals of TRM. Procedures and methods used to adopt and apply TRM are described. Reuse is frequently thought of as only being applicable to code. However, reuse can apply to all products and all phases of the software life cycle. These products include management and quality assurance plans, designs, and testing procedures. Specific examples of successfully reused products are given and future goals are discussed.

  14. Implantation of total body irradiation in radiotherapy

    International Nuclear Information System (INIS)

    Before implementing a treatment technique, the characteristics of the beam under irradiation conditions must be well acknowledged and studied. Each one of the parameters used to calculate the dose has to be measured and validated before its utilization in clinical practice. This is particularly necessary when dealing with special techniques. In this work, all necessary parameters and measurements are described for the total body irradiation implementation in facilities designed for conventional treatments that make use of unconventional geometries to generate desired enlarged field sizes. Furthermore, this work presents commissioning data of this modality at Hospital das Clinicas of Sao Paulo using comparison of three detectors types for measurements of entrance dose during total body irradiation treatment. (author)

  15. Total quality management of cobalt-60 sources

    International Nuclear Information System (INIS)

    Total Quality Management of Cobalt-60 sources by a supplier requires a life cycle approach to source management. This covers various aspects, including design, manufacturing, installation, field inspection, source surveillance and return of cobalt-60 sources at the end of their useful life. The Total Quality Management approach demonstrates a strong industry commitment to the beneficial use of gamma technology for industrial irradiation applications in both developed nations and in those nations who are developing their infrastructure and techniques for the beneficial use of this technology. MDS Nordion continues to demonstrate its support and commitment to the industry by developing and implementing state-of-the-art standards for the safe use of cobalt-60 sources

  16. Pain Management After Total Joint Arthroplasty.

    Science.gov (United States)

    McDonald, Lisa T; Corbiere, Nicole C; DeLisle, Jay A; Clark, Alexander Martin; Kuxhaus, Laurel

    2016-06-01

    Controlling pain after total joint arthroplasty (TJA) is critical to minimizing complications, decreasing costs, and expediting patients' return to function. We implemented a TJA multimodal pain management protocol at a Level III trauma center in a small, rural community in New York. We retrospectively reviewed 266 patient charts and collected patient demographics, pain management information, and discharge data. Our primary goals were to quantify the total number of narcotic medication doses used and length of hospital stay. The multimodal pain management protocol significantly reduced the number of narcotic doses used (P pain management after TJA can reduce narcotic use and hospital length of stay, thereby also reducing the incidence of side effects from narcotics. PMID:27234795

  17. Total economic value of forests in Mexico

    International Nuclear Information System (INIS)

    Failure to account for the numerous functions and economic uses of forests have led to patterns of global forest use with many detrimental environmental consequences. This study demonstrates the economic techniques for estimating the Total Economic Value (TEV) for forests. For the Mexican forest estate, the results show an annual lower bound value of the services of the total forest area to be in the order of USD 4 billion. This aggregate value stems from the nonmarketed services provided by nonconsumptive use; from future potential uses of the genetic resources and from pure existence values; and the largest proportion of economic value coming from the functional values of hydrological and carbon cycling. However, only a proportion of this value can be feasibly be 'captures' within Mexico; much of the benefit of Mexico's forests falls outside the country's borders, and is therefore not considered by forest users or national policy makers. 79 refs, 1 fig, 7 tabs

  18. TOTAL ANTIOXIDANT ACTIVITY OF YEAST SACCHAROMYCES CEREVISIAE

    Directory of Open Access Journals (Sweden)

    Blažena Lavová

    2013-02-01

    Full Text Available Antioxidants are health beneficial compounds that can protect cells and macromolecules (e.g. fats, lipids, proteins and DNA from the damage of reactive oxygen species (ROS. Sacchamomyces cerevisiae are know as organisms with very important antioxidative enzyme systems such as superoxide dismutase or catalase. The total antioxidant activity (mmol Trolox equivalent – TE.g-1 d.w. of Saccharomyces cerevisiae was measured by 2,2´-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid during the yeast cultivation. It was found that the total antioxidant activity was the highest (1.08 mmol TE.g-1 d.w. in the strain Kolín after 32 hours of cultivation and the lowest (0.26 mmol TE.g-1 d.w. in the strain Gyöng after 12 hours of cultivation.

  19. Asymptotic Behaviour of Total Generalised Variation

    KAUST Repository

    Papafitsoros, Konstantinos

    2015-01-01

    © Springer International Publishing Switzerland 2015. The recently introduced second order total generalised variation functional TGV2 β,α has been a successful regulariser for image processing purposes. Its definition involves two positive parameters α and β whose values determine the amount and the quality of the regularisation. In this paper we report on the behaviour of TGV2 β,α in the cases where the parameters α, β as well as their ratio β/α becomes very large or very small. Among others, we prove that for sufficiently symmetric two dimensional data and large ratio β/α, TGV2 β,α regularisation coincides with total variation (TV) regularization

  20. Scientific observations at total solar eclipses

    Institute of Scientific and Technical Information of China (English)

    Jay M.Pasachoff

    2009-01-01

    The occasion of the longest totality of an eclipse in the 18 yr 111/3 d saros cycle leads to taking stock of the scientific value of ground-based eclipse observations in this space age. Though a number of space satellites from the U.S., Europe, Japan, and Russia study the Sun, scientists at eclipses can observe the solar chromosphere and corona at higher spatial resolution, at higher temporal resolution, and at higher spectral resolution than are possible aloft. Furthermore, eclipse expeditions can transport a wide variety of state-of-the-art equipment to the path of totality. Thus, for at least some years to come, solar eclipse observations will remain both scientifically valuable and cost-effective ways to study the outer solar atmosphere.

  1. An unusual case of total ophthalmoplegia

    Directory of Open Access Journals (Sweden)

    Chowdhury Ravindra

    2009-01-01

    Full Text Available An eight-year-old male child presented with drooping of the left eyelid with a history of penetrating injury of hard palate by an iron spoon seven days ago, which had already been removed by the neurosurgeon as the computed tomography scan revealed a spoon in the left posterior ethmoid and sphenoid bone penetrating into the middle cranial fossa. On examination, visual acuity was 20/20 in each eye and left eye showed total ophthalmoplegia. Oral cavity revealed a hole in the left lateral part of the hard palate. We managed the case with tapering dose of systemic prednisolone. The total ophthalmoplegia was markedly improved in one month. Cases of foreign bodies in the orbit with intracranial extension are not unusual, but the path this foreign body traveled through the hard palate without affecting the optic nerve, internal carotid artery or cavernous sinus makes an interesting variation.

  2. Overview of Total Group financial year

    International Nuclear Information System (INIS)

    In 2004, the combination of very high crude oil prices with a strong rise of refining margins, and in the second half of 2004 of the start off again of the rise of petrochemical margins, has led Total Group to reach a record level of 9.04 billion euros for its net adjusted result, which represents a 23% rise with respect to 2003, and this despite a fall of the Dollar exchange rate. Total has also carried on its downstream strategy of natural gas production. This strategy aims at facilitating and optimizing the access to its present day and future productions and reserves, not only to traditional markets but also to markets opened to world competition. (J.S.)

  3. Total Immersion Program学习心得

    Institute of Scientific and Technical Information of China (English)

    郑喜花

    2014-01-01

    经过了本年度的暑假学习生活,真是受益匪浅。在这期间参加了一个Total Immersion Program的学习培训班,在这个培训班中学到了很多东西,也受到了很多的启发。将对在这个培训班所学到的知识和得到的体会分享给大家,为以后从事或者参与这个Total Immersion Program学习时提供借鉴和参考。

  4. Total Cellular RNA Modulates Protein Activity.

    Science.gov (United States)

    Majumder, Subhabrata; DeMott, Christopher M; Reverdatto, Sergey; Burz, David S; Shekhtman, Alexander

    2016-08-16

    RNA constitutes up to 20% of a cell's dry weight, corresponding to ∼20 mg/mL. This high concentration of RNA facilitates low-affinity protein-RNA quinary interactions, which may play an important role in facilitating and regulating biological processes. In the yeast Pichia pastoris, the level of ubiquitin-RNA colocalization increases when cells are grown in the presence of dextrose and methanol instead of methanol as the sole carbon source. Total RNA isolated from cells grown in methanol increases β-galactosidase activity relative to that seen with RNA isolated from cells grown in the presence of dextrose and methanol. Because the total cellular RNA content changes with growth medium, protein-RNA quinary interactions can alter in-cell protein biochemistry and may play an important role in cell adaptation, critical to many physiological and pathological states. PMID:27456029

  5. Temporal bone chondroblastoma totally invisible on MRI.

    Science.gov (United States)

    Hiraumi, Harukazu; Arakawa, Yoshiki; Yamamoto, Norio; Sakamoto, Tatsunori; Ito, Juichi

    2016-08-01

    We report a case of temporal bone chondroblastoma that was totally invisible on MRI. The patient was a 64-year-old man who presented with several months history of vertigo. The CT scan with bone window setting showed destruction of the temporomandibular joint, the floor of the middle cranial fossa, and the superior semicircular canal. Calcific foci were seen within the tumor. On MR imaging, the tumor, situating mainly medial to the temporomandibular joint, showed no signal on both T1- and T2-weighted images. The tumor was not enhanced with gadolinium. In summary, the tumor was totally signal negative or "invisible" on pre- and postcontrast T1- and T2-weighted images. The tumor was resected through transpetrosal - transzygomatic approach. PMID:26743837

  6. Inestabilidad de la Artroplastia Total de Cadera

    OpenAIRE

    Ezquerra Herrando, Laura; Albareda Albareda, Jorge; Seral García, Belén

    2014-01-01

    INTRODUCCIÓN La artroplastia total de cadera (ATC) es un procedimiento muy frecuente en los Servicios de Cirugía Ortopédica y Traumatología, y aunque su efectividad es muy elevada, no está exenta de complicaciones como son el aflojamiento aséptico, luxaciones, infección y fracturas periprotésicas. A pesar de los avances en las técnicas y modelos protésicos, la luxación sigue siendo la segunda complicación más frecuente después del aflojamiento aséptico en las artroplastias totales de cadera. ...

  7. Total Synthesis of (±)-Integrifolin.

    Science.gov (United States)

    Shimomaki, Katsuya; Kusama, Hiroyuki; Iwasawa, Nobuharu

    2016-07-11

    The total synthesis of (±)-integrifolin has been achieved for the first time through the stereoselective preparation of the bicyclo[5.3.0]decane skeleton based on the tungsten-catalyzed cyclization of acyclic trienynes under photoirradiation conditions. Further key transformations of the cyclized product are the Tamao oxidation through cyclic silyl ether, the introduction of two oxygen functionalities by the oxidation of the diene and the construction of three exo-methylene moieties. PMID:27147582

  8. Total Synthesis and Stereochemical Assignment of Callyspongiolide.

    Science.gov (United States)

    Zhou, Jingjing; Gao, Bowen; Xu, Zhengshuang; Ye, Tao

    2016-06-01

    Total synthesis of four callyspongiolide stereoisomers led to unambiguous assignment of relative and absolute stereochemistry of the natural product. Key features of the convergent, fully stereocontrolled route include the use of Krische allylation, Kiyooka Aldol reaction, Kociénski-Julia olefination, Still-Gennari olefination, Yamaguchi macrocyclization, and Sonogashira coupling reaction. Biological evaluation of the synthesized compounds against an array of cancer cells revealed that the stereochemistry of the macrolactone core played an important role. PMID:27227371

  9. Total synthesis of (+)-antroquinonol and (+)-antroquinonol D.

    Science.gov (United States)

    Sulake, Rohidas S; Chen, Chinpiao

    2015-03-01

    The first total synthesis of (+)-antroquinonol and (+)-antroquinonol D, two structurally unique quinonols with a sesquiterpene side chain, is described. The route features an iridium-catalyzed olefin isomerization-Claisen rearrangement reaction (ICR), lactonization, and Grubbs olefin metathesis. The requisite α,β-unsaturation was achieved via the selenylation/oxidation protocol and elimination of β-methoxy group to provide two natural products from a common intermediate. PMID:25679542

  10. Total elbow arthroplasty: a radiographic outcome study

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Xue Susan [University of Washington, Department of Radiology, Box 357115, Seattle, WA (United States); Petscavage-Thomas, Jonelle M. [Penn State Hershey Medical Center, Department of Radiology, Hershey, PA (United States); Ha, Alice S. [University of Washington, Department of Radiology, Box 354755, Seattle, WA (United States)

    2016-06-15

    Total elbow arthroplasty (TEA) is becoming a popular alternative to arthrodesis for patients with end-stage elbow arthrosis and comminuted distal humeral fractures. Prior outcome studies have primarily focused on surgical findings. Our purpose is to determine the radiographic outcome of TEA and to correlate with clinical symptoms such as pain. This is an IRB-approved retrospective review from 2005 to 2015 of all patients with semiconstrained TEA. All available elbow radiographs and clinical data were reviewed. Data analysis included descriptive statistics and Kaplan-Meier survival curves for radiographic and clinical survival. A total of 104 total elbow arthroplasties in 102 patients were reviewed; 75 % were in women and the mean patient age was 63.1 years. Mean radiographic follow-up was 826 days with average of four radiographs per patient. Seventy TEAs (67 %) developed radiographic complications, including heterotopic ossification (48 %), perihardware lucency (27 %), periprosthetic fracture (23 %), hardware subluxation/dislocation (7 %), polyethylene wear (3 %), and hardware fracture/dislodgement (3 %); 56 patients (55 %) developed symptoms of elbow pain or instability and 30 patients (30 %) underwent at least one reoperation. In patients with radiographic complications, 66 % developed elbow pain, compared to 19 % of patients with no radiologic complications (p = 0.001). Of the patients with radiographic complications, 39 % had at least one additional surgery compared to 0 % of patients without radiographic complications (p = 0.056). Radiographic complications are common in patients after total elbow arthroplasty. There is a strong positive association between post-operative radiographic findings and clinical outcome. Knowledge of common postoperative radiographic findings is important for the practicing radiologist. (orig.)

  11. Total Synthesis of (+)-Rubriflordilactone A.

    Science.gov (United States)

    Goh, Shermin S; Chaubet, Guilhem; Gockel, Birgit; Cordonnier, Marie-Caroline A; Baars, Hannah; Phillips, Andrew W; Anderson, Edward A

    2015-10-19

    Two enantioselective total syntheses of the nortriterpenoid natural product rubriflordilactone A are described, which use palladium- or cobalt-catalyzed cyclizations to form the CDE rings, and converge on a late-stage synthetic intermediate. These key processes are set up through the convergent coupling of a common diyne component with appropriate AB-ring aldehydes, a strategy that sets the stage for the synthetic exploration of other members of this family of natural products. PMID:26337920

  12. Counterterrorism and cybersecurity total information awareness

    CERN Document Server

    Lee, Newton

    2013-01-01

    Provides a broad survey of the United States' counterterrorism history, the use of artificial intelligence in data mining, social media and privacy, cyber attacks and prevention, and longstanding issues of war and peace Closely examines how Total Information Awareness, a governmental data mining project focused on scanning public and private data, plays an integral role in cybersecurity Analyzes recent cyberattacks across the globe orchestrated by 'hacktivist' groups, such as Anonymous

  13. Total fact-book 2000-2005

    International Nuclear Information System (INIS)

    TOTAL S.A., a French society incorporated in France on March 28, 1924, together with its subsidiaries and affiliates, is the fourth largest publicly-traded integrated oil and gas company in the world. This document provides statistical data and information on the corporate (highlights, statements), upstream (production, costs,main producing fields, drilling), upstream maps, downstream (refining, distillation, retail gasoline outlets) and chemicals (sales, specialities). (A.L.B.)

  14. Introduction of total knee arthroplasty in Lithuania

    OpenAIRE

    Tarasevicius, Sarunas; Stucinskas, Justinas; Robertsson, Otto; Wingstrand, Hans

    2009-01-01

    Background and purpose We have previously reported that the first 10 years of hip arthroplasty in Lithuania resulted in a higher cumulative revision rate than that observed in Sweden. We thus compared the corresponding results after introduaction of total knee replacement in Lithuania. Methods The 10-year revision rate for the first 595 primary ScanKnee arthroplasties inserted in Klaipeda, Lithuania, was compared to that for the first 1,280 ScanKnee primary arthroplasties inserted in Sweden. ...

  15. Asymptotic behaviour of total generalised variation

    OpenAIRE

    Papafitsoros, Konstantinos; Valkonen, Tuomo

    2015-01-01

    The recently introduced second order total generalised variation functional $\\mathrm{TGV}_{\\beta,\\alpha}^{2}$ has been a successful regulariser for image processing purposes. Its definition involves two positive parameters $\\alpha$ and $\\beta$ whose values determine the amount and the quality of the regularisation. In this paper we report on the behaviour of $\\mathrm{TGV}_{\\beta,\\alpha}^{2}$ in the cases where the parameters $\\alpha, \\beta$ as well as their ratio $\\beta/\\alpha$ becomes very l...

  16. Total Variation Denoising using Iterated Conditional Expectation

    OpenAIRE

    Louchet, Cécile; Moisan, Lionel

    2014-01-01

    We propose a new variant of the celebrated Total Variation image denoising model of Rudin, Osher and Fatemi, which provides results very similar to the Bayesian posterior mean variant (TV-LSE) while showing a much better computational efficiency. This variant is based on an iterative procedure which is proved to converge linearly to a fixed point satisfying a marginal conditional mean property. The implementation is simple, provided numerical precision issues are correctly handled. Experiment...

  17. Fracture of femoral total hip replacement components

    International Nuclear Information System (INIS)

    The biomechanical factors responsible for fatigue fracture of femoral total hip component stems were studied by laboratory loading simulations using implants which were instrumented with strain gauges. Stress levels were low when the prosthesis was rigidly fixed in acrylic along its entire length. Significantly higher stresses were recorded in stems which were loose in the acrylic or which were fixed in their distal portion only

  18. TOTAL ANTIOXIDANT ACTIVITY OF YEAST SACCHAROMYCES CEREVISIAE

    OpenAIRE

    Blažena Lavová; Dana Urminská

    2013-01-01

    Antioxidants are health beneficial compounds that can protect cells and macromolecules (e.g. fats, lipids, proteins and DNA) from the damage of reactive oxygen species (ROS). Sacchamomyces cerevisiae are know as organisms with very important antioxidative enzyme systems such as superoxide dismutase or catalase. The total antioxidant activity (mmol Trolox equivalent – TE.g-1 d.w.) of Saccharomyces cerevisiae was measured by 2,2´-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) during the yeas...

  19. Locally inertial coordinates with totally antisymmetric torsion

    CERN Document Server

    Socolovsky, M

    2010-01-01

    We show that the necessary and sufficient condition for erecting locally inertial coordinates at a point $p$ of a $U^4$-space, and therefore assuring the validity of the equivalence principle at that point, is the vanishing at $p$ of the symmetric part of the contortion tensor. This fact does not demand a vanishing torsion, but only a totally antisymmetric one. As an application, we derive the geodesic deviation equation; and prove the compatibility with the Newtonian limit.

  20. IFQs and total factor productivity changes

    OpenAIRE

    Solis, Daniel; Agar, Juan J.; Corral Cuervo, Julio Florentino de

    2015-01-01

    This study investigates changes in the total factor productivity (TFP) and identifies the main sources of TFP growth following the adoption of an individual fishing quota (IFQ) program in the Gulf of Mexico red snapper commercial fishery. Utilizing an unbalanced panel of 722 vertical line vessels Malmquist indices were derived from an output-oriented stochastic distance frontier. The analysis shows that the IFQ program had a positive impact on the productivity of the fleet and that most of th...