WorldWideScience

Sample records for benzyne-furan cycloadditions total

  1. 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....

  2. 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

  3. Cycloadditions for Studying Nucleic Acids.

    Science.gov (United States)

    Kath-Schorr, Stephanie

    2016-02-01

    Cycloaddition reactions for site-specific or global modification of nucleic acids have enabled the preparation of a plethora of previously inaccessible DNA and RNA constructs for structural and functional studies on naturally occurring nucleic acids, the assembly of nucleic acid nanostructures, therapeutic applications, and recently, the development of novel aptamers. In this chapter, recent progress in nucleic acid functionalization via a range of different cycloaddition (click) chemistries is presented. At first, cycloaddition/click chemistries already used for modifying nucleic acids are summarized, ranging from the well-established copper(I)-catalyzed alkyne-azide cycloaddition reaction to copper free methods, such as the strain-promoted azide-alkyne cycloaddition, tetrazole-based photoclick chemistry and the inverse electron demand Diels-Alder cycloaddition reaction between strained alkenes and tetrazine derivatives. The subsequent sections contain selected applications of nucleic acid functionalization via click chemistry; in particular, site-specific enzymatic labeling in vitro, either via DNA and RNA recognizing enzymes or by introducing unnatural base pairs modified for click reactions. Further sections report recent progress in metabolic labeling and fluorescent detection of DNA and RNA synthesis in vivo, click nucleic acid ligation, click chemistry in nanostructure assembly and click-SELEX as a novel method for the selection of aptamers. PMID:27572987

  4. 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...

  5. Gold-catalyzed oxidative cycloadditions to activate a quinoline framework.

    Science.gov (United States)

    Huple, Deepak B; Ghorpade, Satish; Liu, Rai-Shung

    2013-09-23

    Going for gold! Gold-catalyzed reactions of 3,5- and 3,6-dienynes with 8-alkylquinoline oxides results in an oxidative cycloaddition with high stereospecificity (see scheme; EWG = electron-withdrawing group); this process involves a catalytic activation of a quinoline framework. The reaction mechanism involves the intermediacy of α-carbonyl pyridinium ylides (I) in a concerted [3+2]-cycloaddition with a tethered alkene.

  6. 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.

  7. Functionalization of Graphene via 1,3-Dipolar Cycloaddition

    NARCIS (Netherlands)

    Quintana, Mildred; Spyrou, Konstantinos; Grzelczak, Marek; Browne, Wesley R.; Rudolf, Petra; Prato, Maurizio

    2010-01-01

    Few-layer graphenes (FLG) produced by dispersion and exfoliation of graphite in N-methylpyrrolidone were successfully functionalized using the 1,3-dipolar cycloaddition of azomethine ylides. The amino functional groups attached to graphene sheets were quantified by the Kaiser test. These amino group

  8. Criss-cross Cycloadditions on Ketazines Derived from Alicyclic Ketones

    Directory of Open Access Journals (Sweden)

    Milan Potacek

    2006-01-01

    Full Text Available The reactivity of alicyclic ketazines in criss-cross cycloadditions was investigated. They react with potassium cyanate and ammonium thiocyanate in the presence of acetic acid to form spirocyclic perhydro[1,2,4]triazolo[1,2-a][1,2,4]triazole-1,5-diones and perhydro[1,2,4]triazolo[1,2-a][1,2,4]triazole-1,5-dithiones, respectively, in relatively high yields.

  9. ORGANIC CHEMISTRY. Iron-catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes.

    Science.gov (United States)

    Hoyt, Jordan M; Schmidt, Valerie A; Tondreau, Aaron M; Chirik, Paul J

    2015-08-28

    Cycloadditions, such as the [4+2] Diels-Alder reaction to form six-membered rings, are among the most powerful and widely used methods in synthetic chemistry. The analogous [2+2] alkene cycloaddition to synthesize cyclobutanes is kinetically accessible by photochemical methods, but the substrate scope and functional group tolerance are limited. Here, we report iron-catalyzed intermolecular [2+2] cycloaddition of unactivated alkenes and cross cycloaddition of alkenes and dienes as regio- and stereoselective routes to cyclobutanes. Through rational ligand design, development of this base metal-catalyzed method expands the chemical space accessible from abundant hydrocarbon feedstocks.

  10. 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

  11. 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

  12. 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

  13. 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.

  14. 1, 3-Dipolar Cycloaddition Reaction between Vinyl Acetate and N-Alkyl Hydroxypyridinium Halide

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    1, 3 Dipolar cycloaddition reaction between vinyl acetate and 3-hydroxypyridiniun betaine was performed under solid-liquid phase transfer catalytic condition. This reaction has been successfully used on the synthesis of an analogue of Bao-Gong-Teng A.

  15. 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

  16. Asymmetric metal-catalyzed [3+2] cycloadditions of azomethine ylides

    OpenAIRE

    Stohler, Remo

    2006-01-01

    Cycloadditions of azomethine ylides with olefins provide a short, attractive route to pyrrolidine units with the potential to control the relative and absolute configuration by means of a chiral catalyst. Grigg and co-workers have pioneered the use of chiral transition metal complexes to induce enantioselective cycloadditions of this type. However, stoichiometric amounts of metal complexes were employed in this work. Paying regard to Griggs investigations it was intended to develo...

  17. [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...

  18. 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

  19. 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

  20. 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

  1. 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.

  2. Chemical functionalization of graphene via aryne cycloaddition: a theoretical study.

    Science.gov (United States)

    Zhao, Jing-xiang; Wang, Hong-xia; Gao, Bo; Wang, Xiao-guang; Cai, Qing-hai; Wang, Xuan-zhang

    2012-06-01

    Chemical functionalization of graphene provides a promising route to improve its solubility in water and organic solvents as well as modify its electronic properties, thus significantly expanding its potential applications. In this article, by using density functional theory (DFT) methods, we have studied the effects of the chemical functionalization of graphenes via aryne cycloaddition on its properties. We found that the adsorption of an isolated aryne group on the graphene sheet is very weak with the adsorption energy of -0.204 eV, even though two new single C-C interactions are formed between the aryne group and the graphene. However, the interaction of graphene with the aryne group can be greatly strengthened by (i) substituting the H-atoms in aryne group with F-, Cl-, -NO(2) (electron-withdrawing capability), or CH(3)-group (electron-donating capability), and (ii) increasing the coverage of the adsorbed aryne groups on the graphene sheet. As expected, the strongest bonding is found on the graphene edges, in which the adsorbed aryne groups prefer to be far away from each other. Interestingly, chemical functionalization with aryne groups leads to an opening of the band gap of graphene, which is dependent on the coverage of the adsorbed aryne groups. The present work provides an insight into the modifications of graphene with aryne groups in experiment.

  3. Enantioselective organocatalytic formal [3 + 3]-cycloaddition of alpha,beta-unsaturated aldehydes and application to the asymmetric synthesis of (-)-isopulegol hydrate and (-)-cubebaol.

    Science.gov (United States)

    Hong, Bor-Cherng; Wu, Ming-Fun; Tseng, Hsing-Chang; Liao, Ju-Hsiou

    2006-05-25

    [reaction: see text] The first highly enantioselective organocatalyzed carbo [3 + 3] cascade cycloaddition of alpha,beta-unsaturated aldehydes is reported. Using this methodology, crotonaldehyde is converted to 6-hydroxy-4-methylcyclohex-1-enecarbaldehyde, which is used in the synthesis of (-)-isopulegol hydrate, (-)-cubebaol, and p-tolualdehyde as well as (-)-6-hydroxy-4-methyl-1-cyclohexene-1-methanol acetate, an intermediate in the total synthesis of lycopodium alkaloid magellanine. Other alpha,beta-unsaturated aldehydes give rise to chiral cyclohexadienes via formal [4 + 2] reactions. PMID:16706490

  4. 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

  5. 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.

  6. Monitoring Wnt Protein Acylation Using an In Vitro Cyclo-Addition Reaction

    Science.gov (United States)

    Tuladhar, Rubina; Yarravarapu, Nageswari; Lum, Lawrence

    2016-01-01

    We describe here a technique for visualizing the lipidation status of Wnt proteins using azide-alkyne cycloaddition chemistry (click chemistry) and SDS-PAGE. This protocol incorporates in vivo labeling of a Wnt-IgG Fc fusion protein using an alkynylated palmitate probe but departs from a traditional approach by incorporating a secondary cycloaddition reaction performed on single-step purified Wnt protein immobilized on protein A resin. This approach mitigates experimental noise by decreasing the contribution of labeling from other palmitoylated proteins and by providing a robust method for normalizing labeling efficiency based on protein abundance. PMID:27590147

  7. Asymmetric total synthesis of vindoline.

    Science.gov (United States)

    Kato, Daisuke; Sasaki, Yoshikazu; Boger, Dale L

    2010-03-24

    A concise asymmetric total synthesis of (-)-vindoline (1) is detailed based on a tandem intramolecular [4+2]/[3+2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which the tether linking the initiating dienophile and oxadiazole bears a chiral substituent that controls the facial selectivity of the initiating Diels-Alder reaction and sets absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduces three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. Implementation of the approach also required the development of a unique ring expansion reaction to provide a six-membered ring suitably functionalized for introduction of the Delta (6, 7)-double bond found in the core structure of vindoline and defined our use of a protected hydroxymethyl group as the substituent used to control the stereochemical course of the cycloaddition cascade.

  8. 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...

  9. Development of chiral metal amides as highly reactive catalysts for asymmetric [3 + 2] cycloadditions

    Science.gov (United States)

    Yamashita, Yasuhiro; Yoshimoto, Susumu; Dutton, Mark J

    2016-01-01

    Summary Highly efficient catalytic asymmetric [3 + 2] cycloadditions using a chiral copper amide are reported. Compared with the chiral CuOTf/Et3N system, the CuHMDS system showed higher reactivity, and the desired reactions proceeded in high yields and high selectivities with catalyst loadings as low as 0.01 mol %. PMID:27559396

  10. Cycloadditions in mixed aqueous solvents : the role of the water concentration

    NARCIS (Netherlands)

    Rispens, T; Engberts, JBFN

    2005-01-01

    We examined the kinetics of a series of cycloaddition reactions in mixtures of water with methanol, acetonitrile and poly(ethylene glycol) (MW 1000). The reactions include the Diels-Alder (DA) reaction between cyclopentadiene and N-n-butylmaleimide or acridizinium bromide, the retro-Diels-Alder (RDA

  11. 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.

  12. Phosphoramidite accelerated copper(I)-catalyzed [3+2] cycloadditions of azides and alkynes

    NARCIS (Netherlands)

    Campbell-Verduyn, Lachlan S.; Mirfeizi, Leila; Dierckx, Rudi A.; Elsinga, Philip H.; Feringa, Ben L.

    2009-01-01

    Monodentate phosphoramidite ligands are used to accelerate the copper(I)-catalyzed 1,3-dipolar cycloaddition of azides and alkynes (CuAAC) rapidly yielding a wide variety of functionalized 1,4-disubstituted-1,2,3-triazoles; Cu(I) and Cu(II) salts both function as the copper source in aqueous solutio

  13. 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.

  14. 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.

  15. 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

  16. 1,3-DIPOLAR CYCLOADDITIONS APPROACH TO BIOACTIVE SPIROHETEROCYCLIC COMPOUNDS 1,3-dipolare Cycloadditionen Ansatz zur BIOACTIVE

    Directory of Open Access Journals (Sweden)

    Essam M. Hussein

    2012-10-01

    Full Text Available Spiro compounds represent an important class of naturally occurring substances characterized by highly pronounced biological properties. The most developed avenue for the synthesis of these compounds depends on the cycloaddition to an exocyclic bond. 1,3-dipolar cycloaddition reactions are considered to be one of the most useful processes for the construction of five membered heterocyclic ring systems in highly regio- and stereoselective manner. This review describes 1 general methods for generation and preparation of most important 1,3- dipoles such as nitrones, nitrile oxides and azomethine ylides; and 2 the most recent examples of synthetic applications of 1,3-dipolar cycloaddition reactions to bioactive spiroheterocyclic compounds.

  17. 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

  18. Ceric Ammonium Nitrate-mediated Oxidative Cycloaddition of 1,3-Dicarbonyls to β-Aryl-α,β-unsaturated Ketones

    Institute of Scientific and Technical Information of China (English)

    Wei ZHANG; Cong De HUO; Zheng Gang LIU; Zhong Li LIU

    2004-01-01

    Regio and stereoselective synthesis of substituted dihydrofurans were accomplished by ceric ammonium nitrate mediated oxidative cycloaddition of 1,3-dicarbonyls to β-aryl-α,β-unsaturated ketones in moderate yields.

  19. 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.

  20. "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

  1. A Theoretical Study on the Mechanism of the Cycloaddition Reaction between Alkylidenestannylene and Ethylene

    Institute of Scientific and Technical Information of China (English)

    LU Xiu-Hui; YU Hai-Bin; WU Wei-Rong

    2005-01-01

    The mechanism of a cycloaddition reaction between singlet alkylidenestannylene and ethylene has been investigated with MP2/3-21G* and B3LYP/3-21G* methods, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. Energies for the involved conformations were calculated by CCSD(T)//MP2/3-21G* and CCSD(T)//B3LYP/3-21G* methods, respectively. The results show that the dominant reaction pathway of the cycloaddition is that an intermediate (INT) is firstly formed between the two reactants through a barrier-free exothermic reaction of 39.7 kJ/mol, and the intermediate then isomerizes to a four-membered ring product (P2.1) via a transition state TS2.1 with a barrier of 66.8 kJ/mol.

  2. Unusual Cycloadducts from the Dipolar Cycloaddition of Allenyl Perfluoroalkyl Sulfones to Nitrones

    Institute of Scientific and Technical Information of China (English)

    WANG,Xiao-Jin; LIU,Jin-Tao

    2007-01-01

    The dipolar cycloaddition reaction of allenyl perfluoroalkyl sulfones (1) to nitrones (2) was described. Unlike nonfluorine-containing allenyl sulfones, 1 reacted readily with 2 in ether at room temperature and unusual zwitterionic cycloadducts (3) were obtained in good yields due to the strong electron-withdrawing effect of perfluoroalkyl groups. The structure of 3 was characterized by spectral analyses and X-ray crystallography.

  3. 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)

  4. Copper-catalyzed [3 + 2] cycloaddition of (phenylethynyl)di-p-tolylstibane with organic azides

    Science.gov (United States)

    Yamada, Mizuki; Matsumura, Mio; Uchida, Yuki; Kawahata, Masatoshi; Murata, Yuki; Kakusawa, Naoki; Yamaguchi, Kentaro

    2016-01-01

    Summary Trisubstituted 5-stibano-1H-1,2,3-triazoles were synthesized in moderate to excellent yields by the Cu-catalyzed [3 + 2] cycloaddition of a ethynylstibane with organic azides in the presence of CuBr (5 mol %) under aerobic conditions. The reaction of 5-stibanotriazole with HCl, I2, and NOBF4 afforded 1-benzyl-4-phenyltriazole, 1-benzyl-5-iodo-4-phenyltriazole, and a pentavalent organoantimony compound, respectively. PMID:27559379

  5. 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...

  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. 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...

  8. 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)

  9. 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...

  10. 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

  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. Gold carbenes, gold-stabilized carbocations, and cationic intermediates relevant to gold-catalysed enyne cycloaddition.

    Science.gov (United States)

    Harris, R J; Widenhoefer, R A

    2016-08-21

    Cationic gold complexes in which gold is bound to a formally divalent carbon atom, typically formulated as gold carbenes or α-metallocarbenium ions, have been widely invoked in a range of gold-catalyzed transformations, most notably in the gold-catalyzed cycloisomerization of 1,n-enynes. Although the existence of gold carbene complexes as intermediates in gold-catalyzed transformations is supported by a wealth of indirect experimental data and by computation, until recently no examples of cationic gold carbenes/α-metallocarbenium ions had been synthesized nor had any cationic intermediates generated via gold-catalyzed enyne cycloaddition been directly observed. Largely for this reason, there has been considerable debate regarding the electronic structure of these cationic complexes, in particular the relative contributions of the carbene (LAu(+)[double bond, length as m-dash]CR2) and α-metallocarbenium (LAu-CR2(+)) forms, which is intimately related to the extent of d → p backbonding from gold to the C1 carbon atom. However, over the past ∼ seven years, a number of cationic gold carbene complexes have been synthesized in solution and generated in the gas phase and cationic intermediates have been directly observed in the gold-catalyzed cycloaddition of enynes. Together, these advances provide insight into the nature and electronic structure of gold carbene/α-metallocarbenium complexes and the cationic intermediates generated via gold-catalyzed enyne cycloaddition. Herein we review recent advances in this area. PMID:27146712

  13. 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.

  14. 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

  15. 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

  16. 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.

  17. 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

  18. 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 ...

  19. 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

  20. 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.

  1. Synthesis of isoxazolidines by 1,3-dipolar cycloaddition and their bioactivity

    Institute of Scientific and Technical Information of China (English)

    Cheng Chunsheng; Li Zhinian; Shu Jinyan; Li Tao; Zhang Baoyan

    2006-01-01

    A series of new isoxazolidines was prepared by 1,3-dipolar cycloaddition of different mono-substituted styrenes with 1,3-dipolar compounds that were prepared by the reaction of N-methylhydroxylamine sulfate with aromatic carbonyl substances.This synthetic pathway for the preparation of isoxazolidines was an ideal process of green chemistry.The synthetic products were 5-substituted isoxazolidines and their structures were characterized by mass and NMR (1H-,13C-,COSY,HSQC,and DEPT) spectrometry,and their bioactivity was investigated indicating that some new compounds inhibited Botrytis cinerea effectively.

  2. 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.

  3. Nitrile Oxide-Norbornene Cycloaddition as a Bioorthogonal Crosslinking Reaction for the Preparation of Hydrogels.

    Science.gov (United States)

    Truong, Vinh X; Zhou, Kun; Simon, George P; Forsythe, John S

    2015-10-01

    This communication describes the first application of cycloaddition between an in situ generated nitrile oxide with norbornene leading to a polymer crosslinking reaction for the preparation of poly(ethylene glycol) hydrogels under physiological conditions. Hydrogels with high water content and robust physical strength are readily formed within 2-5 min by a simple two-solution mixing method which allows 3D encapsulation of neuronal cells. This bioorthogonal crosslinking reaction provides a simple yet highly effective method for preparation of hydrogels to be used in bioengineering.

  4. 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...

  5. ARTICLES: Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde

    Science.gov (United States)

    Lu, Xiu-hui; Li, Yong-qing; Xu, Yue-hua; Han, Jun-feng; Shi, Le-yi

    2010-06-01

    Mechanism of the cycloadditional reaction between singlet dichloro-germylidene and formaldehyde has been investigated with MP2/6-31G* method, including geometry optimization, vibrational analysis and energies for the involved stationary points on the potential energy surface. Prom the potential energy profile, we predict that the cycloaddition reaction between singlet dichloro-germylidene and formaldehyde has two competitive dominant reaction pathways, going with the formation of two side products (INT3 and INT4), simultaneously. Both of the two competitive reactions consist of two steps, two reactants firstly form a three-membered ring intermediate INT1 and a twisted four-membered ring intermediate INT2, respectively, both of which are barrier-free exothermic reactions of 41.5 and 72.3 kJ/mol; then INT1 isomerizes to a four-membered ring product P1 via transition state TS1, and INT2 isomerizes to a chlorine-transfer product P2 via transition state TS2, with the barriers of 2.9 and 0.3 kJ/mol, respectively. Simultaneously, P1 and INT2 further react with formaldehyde to form INT3 and INT4, respectively, which are also barrier-free exothermic reaction of 74.9 and 88.1 kJ/mol.

  6. 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.

  7. Activation-strain analysis reveals unexpected origin of fast reactivity in heteroaromatic azadiene inverse-electron-demand diels-alder cycloadditions.

    Science.gov (United States)

    Talbot, Austin; Devarajan, Deepa; Gustafson, Samantha J; Fernández, Israel; Bickelhaupt, F Matthias; Ess, Daniel H

    2015-01-01

    Heteroaromatic azadienes, especially 1,2,4,5-tetrazines, are extremely reactive partners with alkenes in inverse-electron-demand Diels-Alder reactions. Azadiene cycloaddition reactions are used to construct heterocycles in synthesis and are popular as bioorthogonal reactions. The origin of fast azadiene cycloaddition reactivity is classically attributed to the inverse frontier molecular orbital (FMO) interaction between the azadiene LUMO and alkene HOMO. Here, we use a combination of ab initio, density functional theory, and activation-strain model calculations to analyze physical interactions in heteroaromatic azadiene-alkene cycloaddition transition states. We find that FMO interactions do not control reactivity because, while the inverse FMO interaction becomes more stabilizing, there is a decrease in the forward FMO interaction that is offsetting. Rather, fast cycloadditions are due to a decrease in closed-shell Pauli repulsion between cycloaddition partners. The kinetic-thermodynamic relationship found for these inverse-electron-demand cycloadditions is also due to the trend in closed-shell repulsion in the cycloadducts. Cycloaddition regioselectivity, however, is the result of differences in occupied-unoccupied orbital interactions due to orbital overlap. These results provide a new predictive model and correct physical basis for heteroaromatic azadiene reactivity and regioselectivity with alkene dieneophiles.

  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. 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

  10. 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…

  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. 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.

  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. Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

    Science.gov (United States)

    Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

    2016-03-14

    Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

  15. Dinuclear thiazolylidene copper complex as highly active catalyst for azid–alkyne cycloadditions

    Science.gov (United States)

    Schöffler, Anne L; Makarem, Ata; Rominger, Frank

    2016-01-01

    Summary A dinuclear N-heterocyclic carbene (NHC) copper complex efficiently catalyzes azide–alkyne cycloaddition (CuAAC) “click” reactions. The ancillary ligand comprises two 4,5-dimethyl-1,3-thiazol-2-ylidene units and an ethylene linker. The three-step preparation of the complex from commercially available starting compounds is more straightforward and cost-efficient than that of the previously described 1,2,4-triazol-5-ylidene derivatives. Kinetic experiments revealed its high catalytic CuAAC activity in organic solvents at room temperature. The activity increases upon addition of acetic acid, particularly for more acidic alkyne substrates. The modular catalyst design renders possible the exchange of N-heterocyclic carbene, linker, sacrificial ligand, and counter ion. PMID:27559407

  16. 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.

  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. 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

  19. Pseudopterosin synthesis from a chiral cross-conjugated hydrocarbon through a series of cycloadditions.

    Science.gov (United States)

    Newton, Christopher G; Drew, Samuel L; Lawrence, Andrew L; Willis, Anthony C; Paddon-Row, Michael N; Sherburn, Michael S

    2015-01-01

    The pseudopterosins are a family of diterpene marine natural products, which, by virtue of their interesting anti-inflammatory and analgesic properties, have attracted the attentions of many synthetic chemists. The most efficient syntheses reported to date are 14 and 20 steps in the longest linear sequence for chiral pool and enantioselective approaches, respectively, and all start with precursors that are easily mapped onto the natural product structure. Here, we describe an unconventional approach in which a chiral cross-conjugated hydrocarbon is used as the starting material for a series of three cycloadditions. Our approach has led to a significant reduction in the step count required to access these interesting natural products (10 steps chiral pool and 11 steps enantioselective). Furthermore it demonstrates that cross-conjugated hydrocarbons, erroneously considered by many to be too unstable and difficult to handle, are viable precursors for natural product synthesis.

  20. Pseudopterosin synthesis from a chiral cross-conjugated hydrocarbon through a series of cycloadditions

    Science.gov (United States)

    Newton, Christopher G.; Drew, Samuel L.; Lawrence, Andrew L.; Willis, Anthony C.; Paddon-Row, Michael N.; Sherburn, Michael S.

    2015-01-01

    The pseudopterosins are a family of diterpene marine natural products, which, by virtue of their interesting anti-inflammatory and analgesic properties, have attracted the attentions of many synthetic chemists. The most efficient syntheses reported to date are 14 and 20 steps in the longest linear sequence for chiral pool and enantioselective approaches, respectively, and all start with precursors that are easily mapped onto the natural product structure. Here, we describe an unconventional approach in which a chiral cross-conjugated hydrocarbon is used as the starting material for a series of three cycloadditions. Our approach has led to a significant reduction in the step count required to access these interesting natural products (10 steps chiral pool and 11 steps enantioselective). Furthermore it demonstrates that cross-conjugated hydrocarbons, erroneously considered by many to be too unstable and difficult to handle, are viable precursors for natural product synthesis.

  1. Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

    Science.gov (United States)

    Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

    2016-03-14

    Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here. PMID:26687811

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

    Directory of Open Access Journals (Sweden)

    Xiaojun Peng

    2013-01-01

    Full Text Available 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 characterized by FTIR, Raman, XPS, SEM, TEM, and EDS mapping, and the covalent linkage between graphene and tetracyanoethylene oxide was firmly verified. Considering the great diversity of nitrile chemistry, the obtained graphene-TCNEO could be further transformed into other graphene-based derivatives with interesting properties.

  3. 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.

  4. 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.

  5. 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.

  6. 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 ...

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. [3 + 3]-Cycloaddition of Donor-Acceptor Cyclopropanes with Nitrile Imines Generated in Situ: Access to Tetrahydropyridazines.

    Science.gov (United States)

    Garve, Lennart K B; Petzold, Martin; Jones, Peter G; Werz, Daniel B

    2016-02-01

    Donor-acceptor cyclopropanes are reacted under the influence of a Lewis acid with hydrazonyl chlorides to afford tetrahydropyridazines. Formally, this transformation can be regarded as a [3 + 3]-cycloaddition of three-membered rings and nitrile imines generated in situ. This efficient method provides fast access to a variety of structurally diverse pyridazine derivatives. The structure of a typical product was confirmed by X-ray crystallography.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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

  17. Cicloadições [3+4] via cátions oxialílicos: aplicações em sínteses orgânicas [3+4]Cycloadditions via oxyallyl cations: applications in organic synthesis

    Directory of Open Access Journals (Sweden)

    Antônio Jacinto Demuner

    1997-02-01

    Full Text Available Several methodologies for the generation of oxyallyl cations from polybromoketones and other substrates are discussed. The mechanistic aspect of the [3+4] cycloaddition reaction between these cations and dienes leading to the formation of seven membered ring carbocyclic compounds is presented. Finally, some synthetic applications of the [3+4] cycloaddition are shown.

  18. 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.

  19. 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

  20. 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.

  1. Benzofurans as efficient dienophiles in normal electron demand [4 + 2] cycloadditions.

    Science.gov (United States)

    Chopin, Nathalie; Gérard, Hélène; Chataigner, Isabelle; Piettre, Serge R

    2009-02-01

    Dearomatization of electron-poor benzofurans is possible through involvement of the aromatic 2,3-carbon-carbon double bond as dienophile in normal electron demand [4 + 2] cycloadditions. The tricyclic heterocycles thereby produced bear a quaternary center at the cis ring junction, a feature of many alkaloids such as morphine, galanthamine, or lunaridine. The products arising from the reaction have been shown to depend on different factors among which the type of the electron-withdrawing substituent of the benzofuran, the nature of the reacting diene, and the method of activation. In the presence of all-carbon dienes, the reaction yields the expected Diels-Alder adducts. When thermal activation is insufficient, a biactivation associating zinc chloride catalysis and high pressure is required to generate the cycloadducts in good yields and high stereoselectivities, for instance, when cyclohexadiene is involved in the process. The use of more functionalized dienes, such as those bearing alkoxy or silyloxy substituents, also shows the limits of the thermal activation, and hyperbaric conditions are, in this case, well-suited. The involvement of Danishefsky's diene induces a competition in the site of reactivity. The aromatic 2,3-carbon-carbon double bond is unambiguously the most reactive dienophile, and the 3-carbonyl unit becomes a competitive site of reactivity with benzofurans bearing substituents prone to heterocyloaddition, in particular under Lewis acid activation. The sequential involvement of both the aromatic double bond and the carbonyl moiety as dienophiles is then possible by using an excess of diene under high-pressure activation. In line with the experimental results, DFT computations suggest that the Diels-Alder process involving the aromatic double bond is preferred over the hetero-Diels-Alder route through an asynchronous concerted transition state. However, Lewis acid catalysis appears to favor the heterocycloaddition pathway through a stepwise

  2. A modular approach for the construction and modification of glyco-SAMs utilizing 1,3-dipolar cycloaddition.

    Science.gov (United States)

    Kleinert, Mike; Winkler, Tobias; Terfort, Andreas; Lindhorst, Thisbe K

    2008-06-21

    We report the synthesis of a broad variety of functionalized molecules for assembly on gold, allowing the formation of biologically relevant SAMs by a modular approach: either utilizing 1,3-dipolar cycloaddition of alkynes and azides in solution or by 'click on SAM'. Extensive studies into the various parameters of SAM formation and stability have been carried out, leading us to deduce reliable conditions under which glyco-decorated self-assembled monolayers can be formed and studied such as in SPR-supported binding assays.

  3. End-labeled amino terminated monotelechelic glycopolymers generated by ROMP and Cu(I-catalyzed azide–alkyne cycloaddition

    Directory of Open Access Journals (Sweden)

    Ronald Okoth

    2013-03-01

    Full Text Available Functionalizable monotelechelic polymers are useful materials for chemical biology and materials science. We report here the synthesis of a capping agent that can be used to terminate polymers prepared by ring-opening metathesis polymerization of norbornenes bearing an activated ester. The terminating agent is a cis-butene derivative bearing a Teoc (2-trimethylsilylethyl carbamate protected primary amine. Post-polymerization modification of the polymer was accomplished by amidation with an azido-amine linker followed by Cu(I-catalyzed azide–alkyne cycloaddition with propargyl sugars. Subsequent Teoc deprotection and conjugation with pyrenyl isothiocyanates afforded well-defined end-labeled glycopolymers.

  4. Theoretical study on Au(I)-catalyzed [2 + 2 + 2] cycloadditions of ynamides with two discrete nitriles.

    Science.gov (United States)

    Liang, Haosheng; Bi, Siwei; Liu, Yuxia; Tang, Ya-Nan; Liu, Congcong

    2016-03-01

    The Au-catalyzed [2 + 2 + 2] cycloadditions of ynamides with two discrete nitriles were theoretically studied with the aid of DFT calculations. The reaction under consideration is found to start from binding of the catalyst with the ynamide rather than with the nitrile. The Au(i)-ynamide species can effectively induce dimerization of two nitrile molecules while the catalyst only cannot. The Au(i)-ynamide species () is revealed to be more reactive than the Au(i)-nitrile species. Also, the regioselectivity and the influence of EWG vs. EDG involved in the reaction were also rationalized. PMID:26908288

  5. Enantioselective Synthesis of N-PMP-1,2-dihydropyridines via Formal [4 + 2] Cycloaddition between Aqueous Glutaraldehyde and Imines.

    Science.gov (United States)

    Ramaraju, Panduga; Mir, Nisar A; Singh, Deepika; Gupta, Vivek K; Kant, Rajni; Kumar, Indresh

    2015-11-20

    A simple and highly practical one-pot formal [4 + 2] cycloaddition approach for the enantioselective synthesis of N-PMP-1,2-dihydropyridines (DHPs) is described. This chemistry involves an amino-catalytic direct Mannich reaction/cyclization followed by IBX-mediated chemo- and regioselective oxidation sequence between readily available aqueous glutaraldehyde and imines under very mild conditions. A series of N-PMP-1,2-DHPs have been prepared in high yields and excellent enantioselectivity. This method also gives access to both enantiomers of 1,2-DHPs in surplus amount by shifting the catalyst configuration.

  6. 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.

  7. 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.

  8. 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.

  9. Parallel Synthesis of Tetraaryl-4,5-dihydro-1,2,4-triazoles via 1,3-Dipolar Cycloaddition on Soluble Polymer Support

    Institute of Scientific and Technical Information of China (English)

    SHOU,Wang-Ge; WANG,Yan-Guang

    2004-01-01

    @@ The polymer-supported liquid-phase synthesis of small organic molecules has been a subject of intense research activity. 1,2,4-Triazoles are well known for their antifungal[1] and antibacterial[2] activities. This moiety was also found in potent agonist or antagonist receptor lingands. The synthesis of substituted 1,2,4-triazoles via 1,3-dipolar cycloaddition of imines with nitrilimines is well documented.[3] Herein, we would like to report the first liquid-phase synthesis of 1,3,4,5-tetraaryl-4,5-dihydro-1,2,4-triazoles through a 1,3-dipolar cycloaddition of imines with nitrilimines on PEG support.

  10. Tricyclohexylphosphine-Catalyzed Cycloaddition of Enynoates with [60]Fullerene and the Application of Cyclopentenofullerenes as n-Type Materials in Organic Photovoltaics.

    Science.gov (United States)

    Wu, An-Ju; Tseng, Po-Yen; Hsu, Wei-Hsin; Chuang, Shih-Ching

    2016-01-15

    The tricyclohexylphosphine-catalyzed [3 + 2] cycloaddition of (E)-alkyl 5-substituted phenylpent-4-en-2-ynoates with [60]fullerene was studied. This reaction undergoes an initial 1,3-addition of phosphines toward the α-carbons of enynoates. Subsequent cycloaddition of the generated 1,3-dipoles with [60]fullerene and elimination of tricyclohexylphosphines resulted in cyclopentenofullerenes in 20-43% yields. The isolated cyclopentenofullerenes were observed to serve as n-type materials in organic photovoltaics, providing a maximum average power conversion efficiency of 3.79 ± 0.29% upon embedding with P3HT in the active layer.

  11. SPECTRAL AND CHEMICAL MONITORING OF CYCLO-ADDITION REACTION OF CO2 WITH POLY(MMA-co-GMA) COPOLYMERS

    Institute of Scientific and Technical Information of China (English)

    M.Yadollahi; H.Bouhendi; M.J.Zohuriaan-Mehr; K.Kabiri

    2012-01-01

    This paper deals with the monitoring cyclo-addition of CO2 to methyl methacrylate (MMA)-glycidyl methacrylate (GMA) copolymers using spectral (1H-NMR and FTIR) and chemical (elemental analysis and titration) methods.Thus,poly(MMA-co-GMA),was first prepared via solution polymerization.The copolymer was then treated with CO2 gas flow in the presence of cetyltrimethyl ammoniumbromide as a catalyst.In terms of the carbonation reaction time,the terpolymer poly(MMA-co-GMA-co-2-oxo-l,3-dioxolane-4-yl-methyl methacrylate) was prepared in various yield of CO2 fixation (> 90%).The peak intensity changes in the 1H-NMR and FTIR spectra provided excellent demonstrative techniques to monitor the carbonation reaction progression.In a comparative analytical viewpoint,the NMR and elemental analysis were recognized to be the most accurate ways to follow the cyclo-addition reaction progression.However,titration was recognized to be the most preferred method,because it is a very inexpensive,facile and available method with a reasonable costaccuracy balance.

  12. Fluorescent labelling of in situ hybridisation probes through the copper-catalysed azide-alkyne cycloaddition reaction.

    Science.gov (United States)

    Hesse, Susann; Manetto, Antonio; Cassinelli, Valentina; Fuchs, Jörg; Ma, Lu; Raddaoui, Nada; Houben, Andreas

    2016-09-01

    In situ hybridisation is a powerful tool to investigate the genome and chromosome architecture. Nick translation (NT) is widely used to label DNA probes for fluorescence in situ hybridisation (FISH). However, NT is limited to the use of long double-stranded DNA and does not allow the labelling of single-stranded and short DNA, e.g. oligonucleotides. An alternative technique is the copper(I)-catalysed azide-alkyne cycloaddition (CuAAC), at which azide and alkyne functional groups react in a multistep process catalysed by copper(I) ions to give 1,4-distributed 1,2,3-triazoles at a high yield (also called 'click reaction'). We successfully applied this technique to label short single-stranded DNA probes as well as long PCR-derived double-stranded probes and tested them by FISH on plant chromosomes and nuclei. The hybridisation efficiency of differently labelled probes was compared to those obtained by conventional labelling techniques. We show that copper(I)-catalysed azide-alkyne cycloaddition-labelled probes are reliable tools to detect different types of repetitive sequences on chromosomes opening new promising routes for the detection of single copy gene. Moreover, a combination of FISH using such probes with other techniques, e.g. immunohistochemistry (IHC) and cell proliferation assays using 5-ethynyl-deoxyuridine, is herein shown to be easily feasible. PMID:27095480

  13. 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

  14. Adhesion of Photon-Driven Molecular Motors to Surfaces via 1,3-Dipolar Cycloadditions : Effect of Interfacial Interactions on Molecular Motion

    NARCIS (Netherlands)

    Carroll, Gregory T.; London, Gabor; Fernández Landaluce, Tatiana; Rudolf, Petra; Feringa, Ben L.

    2011-01-01

    We report the attachment of altitudinal light-driven molecular motors to surfaces using 1,3-dipolar cycloaddition reactions. Molecular motors were designed containing azide or alkyne groups for attachment to alkyne- or azide-modified surfaces. Surface attachment was characterized by UV-vis, IR, XPS,

  15. 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

  16. Synthesis of isofagomine-pyrrolidine hybrid sugars and analogues of (-)-steviamine and (+)-hyacinthacine C5 using 1,3-dipolar cycloaddition reactions.

    Science.gov (United States)

    Lahiri, Rima; Palanivel, Ashokkumar; Kulkarni, Sudhir A; Vankar, Yashwant D

    2014-11-21

    Highly regioselective 1,3-dipolar cycloadditions between d-arabinose-derived nitrones and d-mannitol-derived trans-olefins have been utilized to synthesize isofagomine-pyrrolidine hybrid sugars, hydroxymethylated analogues of (-)-steviamine and analogues of (+)-hyacinthacine C5. All of the new compounds were subsequently tested against several commercially available glycosidases, and some of them showed good and selective glycosidase inhibition.

  17. 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.

  18. 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.

  19. Asymmetric preparation of polysubstituted cyclopentanes by synergistic Pd(0)/amine catalyzed formal [3+2] cycloadditions of vinyl cyclopropanes with enals.

    Science.gov (United States)

    Laugeois, Maxime; Ponra, Sudipta; Ratovelomanana-Vidal, Virginie; Michelet, Véronique; Vitale, Maxime R

    2016-04-18

    We report herein a novel diastereo- and enantiocontrolled preparation of polysubstituted cyclopentanes by the formal [3+2] cycloadditions of vinyl cyclopropanes with enals. In constrast with previously developed strategies, our original approach is based on the synergistic merger of iminium/enamine organocatalysis with palladium(0) catalysis. PMID:27005726

  20. 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.

  1. Synthesis of [F-18]RGD-K5 by catalyzed [3+2] cycloaddition for imaging integrin alpha(v)beta(3) expression in vivo

    NARCIS (Netherlands)

    Mirfeizi, Leila; Walsh, Joe; Kolb, Hartmuth; Campbell-Verduyn, Lachlan; Dierckx, Rudi A.; Feringa, Ben L.; Elsinga, Philip H.; de Groot, Tjibbe; Sannen, Ivan; Bormans, Guy; Celen, Sofie

    2013-01-01

    In the last few years click chemistry reactions, and in particular copper-catalyzed cycloadditions have been used extensively for the preparation of new bioconjugated molecules such as F-18-radiolabeled radiopharmaceuticals for positron emission tomography (PET). This study is focused on the synthes

  2. Total Thyroidectomy

    Directory of Open Access Journals (Sweden)

    Lopez Moris E

    2016-06-01

    Full Text Available Total thyroidectomy is a surgery that removes all the thyroid tissue from the patient. The suspect of cancer in a thyroid nodule is the most frequent indication and it is presume when previous fine needle puncture is positive or a goiter has significant volume increase or symptomes. Less frequent indications are hyperthyroidism when it is refractory to treatment with Iodine 131 or it is contraindicated, and in cases of symptomatic thyroiditis. The thyroid gland has an important anatomic relation whith the inferior laryngeal nerve and the parathyroid glands, for this reason it is imperative to perform extremely meticulous dissection to recognize each one of these elements and ensure their preservation. It is also essential to maintain strict hemostasis, in order to avoid any postoperative bleeding that could lead to a suffocating neck hematoma, feared complication that represents a surgical emergency and endangers the patient’s life.It is essential to run a formal technique, without skipping steps, and maintain prudence and patience that should rule any surgical act.

  3. Donor/Acceptor-Stabilized 1-Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction.

    Science.gov (United States)

    Reyes, Morelia Lopez; Troadec, Thibault; Rodriguez, Ricardo; Baceiredo, Antoine; Saffon-Merceron, Nathalie; Branchadell, Vicenç; Kato, Tsuyoshi

    2016-07-11

    The reaction of silacyclopropylidene 1 with benzaldehyde generates a 1-silaketene complex 2 by a formal atomic silicon insertion into the C=O bond of the aldehyde. The highly reactive 1-silaketene 2 undergoes a reversible [2+2] cycloaddition with pyridine to give sila-β-lactam 3. Of particular interest, in the presence of 4-dimethylaminopyridine (DMAP), 1-silaketene complex 2 evolves through an intramolecular olefin metathesis reaction, generating a new 1-silaketene complex 8 and cis-stilbene. Theoretical studies suggest that the reaction proceeds through the formation of a transient silacyclobutanone, a four-membered-ring intermediate, similar to that proposed by Chauvin and co-workers for the transition-metal-based olefin metathesis. PMID:27276000

  4. 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.

  5. Donor/Acceptor-Stabilized 1-Silaketene: Reversible [2+2] Cycloaddition with Pyridine and Evolution by an Olefin Metathesis Reaction.

    Science.gov (United States)

    Reyes, Morelia Lopez; Troadec, Thibault; Rodriguez, Ricardo; Baceiredo, Antoine; Saffon-Merceron, Nathalie; Branchadell, Vicenç; Kato, Tsuyoshi

    2016-07-11

    The reaction of silacyclopropylidene 1 with benzaldehyde generates a 1-silaketene complex 2 by a formal atomic silicon insertion into the C=O bond of the aldehyde. The highly reactive 1-silaketene 2 undergoes a reversible [2+2] cycloaddition with pyridine to give sila-β-lactam 3. Of particular interest, in the presence of 4-dimethylaminopyridine (DMAP), 1-silaketene complex 2 evolves through an intramolecular olefin metathesis reaction, generating a new 1-silaketene complex 8 and cis-stilbene. Theoretical studies suggest that the reaction proceeds through the formation of a transient silacyclobutanone, a four-membered-ring intermediate, similar to that proposed by Chauvin and co-workers for the transition-metal-based olefin metathesis.

  6. The 1,3-dipolar cycloaddition reaction of chiral carbohydrate-derived nitrone and olefin: towards long-chain sugars.

    Science.gov (United States)

    Oukani, Hassan; Pellegrini-Moïse, Nadia; Jackowski, Olivier; Chrétien, Françoise; Chapleur, Yves

    2013-11-15

    The thermal and microwave-activated 1,3-dipolar cycloadditions of several α,β-unsaturated esters derived from d-mannose and chiral nitrones derived from threitol have been studied as a model reaction en route to eleven carbon long chain carbohydrates. Very high facial selectivity is observed for the chiral nitrones whereas the olefin facial selectivity varies with the substrate. The presence of a dioxolane ring α to the olefinic bond is beneficial to the facial selectivity of the olefin whereas a pyranose ring is not. The combination of a d-mannose derivative and a l-threitol-derived nitrone is a matched pair suitable for the synthesis of long chain sugars with nine contiguous chiral centres. Finally complete facial selectivity was observed with exo-glycals which gave a single cycloadduct.

  7. The chemistry of simple alkene molecules on Si(100)c(4 × 2): The mechanism of cycloaddition and their selectivities

    Science.gov (United States)

    Akagi, Kazuto; Yoshinobu, Jun

    2016-10-01

    The chemistry of simple alkene molecules on the Si(100) surface is reviewed with the newly-produced visual presentation by theoretical calculations. The early pioneering studies by the Kyoto Group and Pittsburgh group reported the di-σ bond formation and the precursor-mediated chemisorption for acetylene and ethylene on Si(100), respectively. Thereafter, these studies have been stimulating various studies of organic molecules on Si surfaces. Our recent studies have observed the precursor states for alkene chemisorption and elucidated the microscopic mechanisms of the di-σ bond formation (cycloaddition) with the help of theoretical calculations; the site-, stereo- and regio-selective chemisorption of simple alkene molecules on Si(100)c(4 × 2) has been established.

  8. Silver-catalysed azide-alkyne cycloaddition (AgAAC): assessing the mechanism by density functional theory calculations

    Science.gov (United States)

    Banerji, Biswadip; Chandrasekhar, K.; Killi, Sunil Kumar; Pramanik, Sumit Kumar; Uttam, Pal; Sen, Sudeshna; Maiti, Nakul Chandra

    2016-09-01

    `Click reactions' are the copper catalysed dipolar cycloaddition reaction of azides and alkynes to incorporate nitrogens into a cyclic hydrocarbon scaffold forming a triazole ring. Owing to its efficiency and versatility, this reaction and the products, triazole-containing heterocycles, have immense importance in medicinal chemistry. Copper is the only known catalyst to carry out this reaction, the mechanism of which remains unclear. We report here that the `click reactions' can also be catalysed by silver halides in non-aqueous medium. It constitutes an alternative to the well-known CuAAC click reaction. The yield of the reaction varies on the type of counter ion present in the silver salt. This reaction exhibits significant features, such as high regioselectivity, mild reaction conditions, easy availability of substrates and reasonably good yields. In this communication, the findings of a new catalyst along with the effect of solvent and counter ions will help to decipher the still obscure mechanism of this important reaction.

  9. 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.

  10. Discovery of TNF inhibitors from a DNA-encoded chemical library based on diels-alder cycloaddition.

    Science.gov (United States)

    Buller, Fabian; Zhang, Yixin; Scheuermann, Jörg; Schäfer, Juliane; Bühlmann, Peter; Neri, Dario

    2009-10-30

    DNA-encoded chemical libraries are promising tools for the discovery of ligands toward protein targets of pharmaceutical relevance. DNA-encoded small molecules can be enriched in affinity-based selections and their unique DNA "barcode" allows the amplification and identification by high-throughput sequencing. We describe selection experiments using a DNA-encoded 4000-compound library generated by Diels-Alder cycloadditions. High-throughput sequencing enabled the identification and relative quantification of library members before and after selection. Sequence enrichment profiles corresponding to the "bar-coded" library members were validated by affinity measurements of single compounds. We were able to affinity mature trypsin inhibitors and identify a series of albumin binders for the conjugation of pharmaceuticals. Furthermore, we discovered a ligand for the antiapoptotic Bcl-xL protein and a class of tumor necrosis factor (TNF) binders that completely inhibited TNF-mediated killing of L-M fibroblasts in vitro.

  11. 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.

  12. Ceric Ammonium Nitrate-Mediated Oxidative Cycloaddition of 1,3-Dicarbonyls to β-Aryl-α, β-unsaturated Ketones

    Institute of Scientific and Technical Information of China (English)

    ZHANG Wei; HUO Cong-De; LIU Zheng-Gang; LIU Zhong-Li

    2003-01-01

    @@ Oxidative addition of carbon-centred radicals to alkenes mediated by metal salts ( MnⅢ, CeⅣ, HgⅡ,PdⅣ, AgⅠ,and CuⅡ) has received considerable attention over last decade in organic synthesis for construction of carbon-carbon bond. [1,2] Among them, manganese(Ⅲ) acetate and ceric(Ⅳ) ammonium nitrate (CAN) have been use most efficiently. Recently, CAN-mediated oxidative cycloaddition of 1,3-dicarbonyl compounds to alkenes, conjugated compounds, enol silyl ethers and alkynes, has been studied extensively. We exploited that the CAN-mediated oxidative cycloaddition of 1,3-dicarbonyl compounds to β-aryl-α,β-unsaturated ketones afforded dihydrofuran derivatives in moderate yields. All the products were characterized by 1H NMR, 13C NMR, MS and HRMS spectra.

  13. 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.

  14. 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)

  15. Synthetic Studies on Bioactive Natural Polyketides: Intramolecular Nitrile Oxide-Olefin Cycloaddition Approach for Construction of a Macrolactone Skeleton of Macrosphelide B

    Directory of Open Access Journals (Sweden)

    Seung-Mann Paek

    2011-06-01

    Full Text Available Studies on the synthesis of macrosphelide B via an intramolecular nitrile oxide-olefin cycloaddition (INOC is described. In particular, an asymmetric INOC approach using phase transfer catalysts seems to be a potentially efficient and versatile procedure for the construction of the macrolactone skeleton of macrosphelide B in terms of facial selectivity. Our preliminary and unprecedented stereoselective procedure is anticipated to be usefully applied through further studies for the synthesis of the macrosphelide family.

  16. Exploiting the Distal Reactivity of Indolyl Methylenemalononitriles: An Asymmetric Organocatalyzed [4+2] Cycloaddition with Enals Enables the Assembly of Elusive Dihydrocarbazoles.

    Science.gov (United States)

    Rassu, Gloria; Curti, Claudio; Zambrano, Vincenzo; Pinna, Luigi; Brindani, Nicoletta; Pelosi, Giorgio; Zanardi, Franca

    2016-08-26

    An unprecedented technique for the in situ generation of indolyl ortho-quinodimethanes from 2-methylindole-based methylenemalononitriles by amine-mediated remote C(sp(3) )-H deprotonation was developed. These intermediates were efficiently trapped by diverse enals to provide a rapid entry to 2,9-dihydro-1H-carbazole-3-carboxyaldehyde structures through a formal asymmetric [4+2] eliminative cycloaddition governed by a α,α-diphenylprolinol trimethylsilyl ether catalyst.

  17. 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....

  18. 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

  19. Synthesis of novel steroidal 17α-triazolyl derivatives via Cu(I)-catalyzed azide-alkyne cycloaddition, and an evaluation of their cytotoxic activity in vitro.

    Science.gov (United States)

    Frank, Éva; Molnár, Judit; Zupkó, István; Kádár, Zalán; Wölfling, János

    2011-01-01

    Regioselective Cu(I)-catalyzed 1,3-dipolar cycloaddition of steroidal 17α-azides with different terminal alkynes afforded novel 1,4-disubstituted triazolyl derivatives in good yields in both the estrone and the androstane series. The antiproliferative activities of the structurally related triazoles were determined in vitro on three malignant human cell lines (HeLa, MCF7 and A431), with the microculture tetrazolium assay. PMID:21600229

  20. 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

  1. 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

  2. Novel carbamoyl type quinine and quinidine based chiral anion exchangers implementing alkyne-azide cycloaddition immobilization chemistry.

    Science.gov (United States)

    Hettegger, Hubert; Kohout, Michal; Mimini, Vebi; Lindner, Wolfgang

    2014-04-11

    The synthesis and chromatographic evaluation of a series of new Cinchona derived chiral weak anion exchangers is presented. Huisgen Cu(I) mediated alkyne-azide cycloaddition, so-called click chemistry, was used as an immobilization strategy. In this way it was possible to immobilize about 90% of offered selector via 1,2,3-triazole linker, which displays a more efficient way of binding the selector to modified silica compared to common radical mediated thiol-ene addition. Problems associated with potential radical scavenging properties of chiral selectors thereby could be circumvented. The evaluation of the synthesized chiral stationary phases regarding chromatographic behavior was carried out using polar organic mode mobile phase composition and a set of representative chiral organic acids. Different loading densities revealed an optimum selector density of about 310μmol/g chiral stationary phase with respect to resolution and selectivity. A decrease of performance was observed for higher loading, indicating mutual spatial influence of selector units leading to sterical hindrance. In addition, we observed that the effect of free azide groups on retention is negligible and the overall chromatographic behavior is comparable to other Cinchona derived chiral stationary phases.

  3. 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.

  4. One-pot sequential alkynylation and cycloaddition: regioselective construction and biological evaluation of novel benzoxazole-triazole derivatives.

    Science.gov (United States)

    Srivastava, Ananya; Aggarwal, Leena; Jain, Nidhi

    2015-01-12

    Individually, benzoxazole and triazole moieties are of significant biological interest owing to their importance in drugs and pharmaceuticals. To assess their combined biological impact when woven into one molecule, we designed a novel, regioselective, multicomponent, one-pot (MCOP) approach for the construction of benzoxazole-linked triazoles. The synthesis has been achieved in two sequential steps involving copper-catalyzed alkynylation of benzoxazole followed by a 1,3-dipolar cycloaddition reaction. By combination of these two bioactive units into one core, a series of new benzoxazole-triazole scaffolds has been synthesized and subjected to in vitro antibacterial and anticancer evaluation. Tests against clinical isolates of Staphylococcus aureus and Escherichia coli showed potent Gram-negative activity for compounds 4{1,1,1}, 4{1,1,4}, and 4{1,2,1}. The cytotoxicity of the synthesized library was determined against three cancer cell lines: HeLa, SKBr3, and Hep G2. Compound 4{2,2,2} showed significant cytotoxicity against all the cell lines. These preliminary bioassay evaluations strongly suggest the promise and scope of these novel molecules as therapeutic agents in medical science.

  5. N-(furfural) chitosan hydrogels based on Diels-Alder cycloadditions and application as microspheres for controlled drug release.

    Science.gov (United States)

    Montiel-Herrera, Marcelino; Gandini, Alessandro; Goycoolea, Francisco M; Jacobsen, Neil E; Lizardi-Mendoza, Jaime; Recillas-Mota, Maricarmen; Argüelles-Monal, Waldo M

    2015-09-01

    In this study, chitosan was chemically modified by reductive amination in a two-step process. The synthesis of N-(furfural) chitosan (FC) was confirmed by FT-IR and (1)H NMR analysis, and the degrees of substitution were estimated as 8.3 and 23.8%. The cross-linkable system of bismaleimide (BM) and FC shows that FC shared properties of furan-maleimide chemistry. This system produced non-reversible hydrogel networks by Diels-Alder cycloadditions at 85 °C. The system composed of BM and FC (23.8% substitution) generated stronger hydrogel networks than those of FC with an 8.3% degree of substitution. Moreover, the FC-BM system was able to produce hydrogel microspheres. Environmental scanning electron microscopy revealed the surface of the microspheres to be non-porous with small protuberances. In water, the microspheres swelled, increasing their volume by 30%. Finally, microspheres loaded with methylene blue were able to release the dye gradually, obeying second-order kinetics for times less than 600 min. This behavior suggests that diffusion is governed by the relaxation of polymer chains in the swelled state, thus facilitating drug release outside the microspheres.

  6. Ab initio Study of Mechanism of Cycloaddition Reaction be- tween Germylene Silylene (H2Ge=Si:) and Acetone%Ab initio Study of Mechanism of Cycloaddition Reaction be- tween Germylene Silylene (H2Ge=Si:) and Acetone

    Institute of Scientific and Technical Information of China (English)

    Lu, Xiuhui; Han, Junfeng; Li, Yongqing; Wang, Zhina

    2011-01-01

    The mechanism of the cycloaddition reaction between singlet germylene silylene (H2Ge =Si:) and acetone has been investigated with CCSD(T)/6-31G*//MP2/6-31 G* method. From the potential energy profile, we could predict that the reaction has two competitive dominant reaction channels. The present rule of this reaction is that the [2 +2] cycloaddition reaction of the two π-bonds in germylene silylene and acetone generates a four-membered ring silylene with Ge. Because of the unsaturated property of Si atom in the four-membered ring silylene with Ge, it could further react with acetone, resulting in the generation of a bis-heterocyclic compound with Si and Ge. Simul- taneously, the ring strain of the four-membered ring silylene with Ge makes it isomerize to a twisted four-membered ring product.

  7. Copper-free azide-alkyne cycloaddition of targeting peptides to porous silicon nanoparticles for intracellular drug uptake.

    Science.gov (United States)

    Wang, Chang-Fang; Mäkilä, Ermei M; Kaasalainen, Martti H; Liu, Dongfei; Sarparanta, Mirkka P; Airaksinen, Anu J; Salonen, Jarno J; Hirvonen, Jouni T; Santos, Hélder A

    2014-01-01

    Porous silicon (PSi) has been demonstrated as a promising drug delivery vector for poorly water-soluble drugs. Here, a simple and efficient method based on copper-free click chemistry was used to introduce targeting moieties to PSi nanoparticles in order to enhance the intracellular uptake and tumor specific targeting hydrophobic drug delivery. Two RGD derivatives (RGDS and iRGD) with azide-terminated groups were conjugated to bicyclononyne-functionalized PSi nanoparticles via copper-free azide-alkyne cycloaddition. The surface functionalization was performed in aqueous solution at 37 °C for 30 min resulting in conjugation efficiencies of 15.2 and 3.4% (molar ratios) and the nanoparticle size increased from 165.6 nm to 179.6 and 188.8 nm for RGDS and iRGD, respectively. The peptides modification enhanced the cell uptake efficiency of PSi nanoparticles in EA.hy926 cells. PSi-RGDS and PSi-iRGD nanoparticles loaded with sorafenib showed a similar trend for the in vitro antiproliferation activity compared to sorafenib dissolved in dimethyl sulfoxide. Furthermore, sorafenib-loaded PSi-RGDS deliver the drug intracellulary efficiently due to the higher surface conjugation ratio, resulting in enhanced in vitro antiproliferation effect. Our results highlight the surface functionalization methodology for PSi nanoparticles applied here as a universal method to introduce functional moieties onto the surface of PSi nanoparticles and demonstrate their potential active targeting properties for anticancer drug delivery.

  8. Kinetics of bulk photo-initiated copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) polymerizations†

    Science.gov (United States)

    Song, Han Byul; Baranek, Austin; Bowman, Christopher N.

    2016-01-01

    Photoinitiation of polymerizations based on the copper(i)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction enables spatio-temporal control and the formation of mechanically robust, highly glassy photopolymers. Here, we investigated several critical factors influencing photo-CuAAC polymerization kinetics via systematic variation of reaction conditions such as the physicochemical nature of the monomers; the copper salt and photoinitiator types and concentrations; light intensity; exposure time and solvent content. Real time Fourier transform infrared spectroscopy (FTIR) was used to monitor the polymerization kinetics in situ. Six different di-functional azide monomers and four different tri-functional alkyne monomers containing either aliphatic, aromatic, ether and/or carbamate substituents were synthesized and polymerized. Replacing carbamate structures with ether moieties in the monomers enabled an increase in conversion from 65% to 90% under similar irradiation conditions. The carbamate results in stiffer monomers and higher viscosity mixtures indicating that chain mobility and diffusion are key factors that determine the CuAAC network formation kinetics. Photoinitiation rates were manipulated by altering various aspects of the photo-reduction step; ultimately, a loading above 3 mol% per functional group for both the copper catalyst and the photoinitiator showed little or no rate dependence on concentration while a loading below 3 mol% exhibited 1st order rate dependence. Furthermore, a photoinitiating system consisting of camphorquinone resulted in 60% conversion in the dark after only 1 minute of 75 mW cm−2 light exposure at 400–500 nm, highlighting a unique characteristic of the CuAAC photopolymerization enabled by the combination of the copper(i)’s catalytic lifetime and the nature of the step-growth polymerization. PMID:27429650

  9. 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.

  10. 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.

  11. A conceptual DFT approach towards analysing feasibility of the intramolecular cycloaddition Diels-Alder reaction of triene amide in Lewis acid catalyst

    Indian Academy of Sciences (India)

    ABDELILAH BENALLOU; HABIB EL ALAOUI EL ABDALLAOUI; HOCINE GARMES

    2016-09-01

    The effect of Lewis acid catalysts, TiCl₄ and Et₂AlCl on the intramolecular cycloaddition Diels- Alder (IMDA) reaction of triene-amide have been studied theoretically using the DFT (Density Functional Theory) at the 6-31G(d,p) level of theory. The results obtained using the polar model of Domingo, electrophilicity, nucleophilicity indices and thermochemistry computations, demonstrate that these catalysts are coordinated with more nucleophilic atoms of diene fragment (nitrogen and oxygen of amide group). These catalysts affect negatively the feasibility of the reaction as well as the physico-chemical parameters of the IMDA reaction of triene-amide.

  12. 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...

  13. 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.

  14. Application of Cu(I)-catalyzed azide–alkyne cycloaddition for the design and synthesis of sequence specific probes targeting double-stranded DNA

    Science.gov (United States)

    Filichev, Vyacheslav V; Boutorine, Alexandre S

    2016-01-01

    Summary Efficient protocols based on Cu(I)-catalyzed azide–alkyne cycloaddition were developed for the synthesis of conjugates of pyrrole–imidazole polyamide minor groove binders (MGB) with fluorophores and with triplex-forming oligonucleotides (TFOs). Diverse bifunctional linkers were synthesized and used for the insertion of terminal azides or alkynes into TFOs and MGBs. The formation of stable triple helices by TFO-MGB conjugates was evaluated by gel-shift experiments. The presence of MGB in these conjugates did not affect the binding parameters (affinity and triplex stability) of the parent TFOs. PMID:27559384

  15. 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...

  16. 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.

  17. Theoretical Study of the Mechanism of Cycloaddition Reaction between Silylene Silylene (H2Si=Si:) and Acetone

    Institute of Scientific and Technical Information of China (English)

    汪智娜; 时乐义; 李永庆; 卢秀慧

    2012-01-01

    The mechanism of the cycloaddition reaction between singlet silylene silylene (H2Si = Si:) and acetone has been investigated with the CCSD (T)//MP2/6-31 G* method, According to the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction channels. The present rule of this reaction is that the [2 + 2] cycloaddition reaction of the two ~-bonds in silylene silylene (H2Si=Si:) and acetone leads to the formation of a four-membered ring silylene (E3). Because of the unsaturated property of Si: atom in E3, it further reacts with ace- tone to form a silicic bis-heterocyclic compound (P7). Simultaneously, the ring strain of the four-membered ring silylene (E3) makes it isomerize to a twisted four-membered ring product (P4).

  18. 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.

  19. 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

  20. Restricted total stability and total attractivity

    Directory of Open Access Journals (Sweden)

    Giuseppe Zappala'

    2006-08-01

    Full Text Available In this paper the new concepts of restricted total stability and total attractivity is formulated. For this purpose the classical theory of Malkin with suitable changes and the theory of limiting equations, introduced by Sell developed by Artstein and Andreev, are used. Significant examples are presented.

  1. [3+2] Cycloadditions of 1-halo-1-nitroethenes with (Z-C-(3,4,5-trimethoxyphenyl-N-methyl-nitrone as regio- and stereocontrolled source of novel bioactive compounds: preliminary studies

    Directory of Open Access Journals (Sweden)

    Radomir Jasiński

    2016-07-01

    Full Text Available Preliminary experiments shows, that [3+2] cycloadditions reactions proceeds with full regioselectivity and high stereoselectivity. In consequence, 3,4-trans-2-methyl-3-(3,4,5-trimethoxyphenyl-4-halo-4-nitroisoxazolidines are forming as predominantly (or sole products. Additionally, prognosis for the synthesized compounds to be potential ingredients of drugs is good.

  2. 1,3-Dipolar cycloadditions of ethoxycarbonyl-nitrile benzylimine and synthesis of ß-amino acids. Synthesis and reactions of ethyl 2-chloro-2-ethoxyacetate and 2-chloro-2-ethoxyacetylchloride

    DEFF Research Database (Denmark)

    Bach, K.K.; El-Seedi, H.R.; Jensen, H.M.;

    1994-01-01

    The principles of 1,2-cyano-hydroxylation of olefins were applied to the preparation of 1,2-cyano-amines. The dipole component of this cycloaddition was nitrile imines, which formed pyrazolines with olefins. Ring cleavage was accomplished by thermolysis of 3-carboxypyrazolines, which gave 1,2-cya...

  3. 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.

  4. Qualidade total do produto Products total quality

    Directory of Open Access Journals (Sweden)

    Henrique Silveira de Almeida

    1992-06-01

    Full Text Available O texto aborda o conceito de qualidade total do produto, seus determinantes, bem como as dimensões que compõem essa qualidade. Parte-se do pressuposto de que a qualidade do produto deve ser avaliada pela satisfação total do consumidor. Para o consumidor a qualidade do produto envolve pelo menos as seguintes dimensões: a qualidade do produto em si; a qualidade do produto ao longo do tempo; a qualidade dos serviços associados ao uso do produto; e o custo do ciclo de vida do produto. O trabalho procura detalhar e discutir cada uma dessas dimensões da qualidade, tendo em vista a satisfação do consumidor.The paper concerns to the concept of product's total quality, its determinants, and the dimensions wich constitute this quality. We admit that product quality should be evaluated via consumer's total satisfaction. Product quality for consumers includes at least the following dimensions: the product quality per se; the performance of product quality over time; the quality of services related to the use of the product; and the product lifecycle costs. This study seeks to specify and to discuss each of these quality dimensions related to consumer's satisfaction.

  5. 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 ...

  6. 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 ...

  7. 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 ...

  8. 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 ...

  9. 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.

  10. 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.

  11. Synthesis of ferrocenyl-substituted 1,3-dithiolanes via [3 + 2]-cycloadditions of ferrocenyl hetaryl thioketones with thiocarbonyl S-methanides

    Science.gov (United States)

    Hamera-Fałdyga, Róża; Linden, Anthony; Heimgartner, Heinz

    2016-01-01

    Summary Ferrocenyl hetaryl thioketones react smoothly with in situ generated thiocarbonyl S-methanides to give 1,3-dithiolanes. In the case of aromatic S-methanides, the sterically more crowded 4,4,5,5-tetrasubstituted 1,3-dithiolanes (2-CH2 isomers) were formed as sole products. The reactions with cycloaliphatic S-methanides led to mixtures of 2-CH2 and 5-CH2 isomers with the major component being the sterically more crowded 2-CH2 isomers. The preferred formation of the latter products is explained by the assumption that the formal [3 + 2]-cycloadducts were formed via a stepwise reaction mechanism with a stabilized 1,5-diradical as a key intermediate. The complete change of the reaction mechanism toward the concerted [3 + 2]-cycloaddition was observed in the reaction of a sterically crowded cycloaliphatic thiocarbonyl ylide with ferrocenyl methyl thioketone. PMID:27559392

  12. 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.

  13. 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

  14. 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.

  15. Synthetic scope and DFT analysis of the chiral binap–gold(I complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

    Directory of Open Access Journals (Sweden)

    María Martín-Rodríguez

    2013-11-01

    Full Text Available The 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(Sa-Binap·AuTFA]2. The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

  16. 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.

  17. Ultrasonic Synthesis, Molecular Structure and Mechanistic Study of 1,3-Dipolar Cycloaddition Reaction of 1-Alkynylpyridinium-3-olate and Acetylene Derivatives

    Directory of Open Access Journals (Sweden)

    Asmaa Aboelnaga

    2016-06-01

    Full Text Available Regioselectively, ethyl propiolate reacted with 1-(propergyl-pyridinium-3-olate to give two regioisomers; ethyl 4-oxo-8-(prop-2-ynyl-8-aza-bicyclo(3.2.1octa-2,6-diene-6-carboxylate 4, ethyl 2-oxo-8-(prop-2-ynyl-8-aza-bicyclo(3.2.1octa-3,6-diene-6-carboxylate 5 as well as ethyl 2,6-dihydro-6-(prop-2-ynylfuro(2,3-cpyridine-3-carboxylate 6. The obtained compounds were identified by their spectral (IR, mass and NMR data. Moreover, DFT quantum chemical calculations were used to study the mechanism of the cycloaddition reaction. The regioselectivity was explained using transition state calculations, where the calculations agreed with the formation of products 4 and 5 in almost the same ratio. The reaction was also extended for diphenylaceylene as dipolarophile to give only two products instead of three.

  18. 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....

  19. 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...

  20. 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...

  1. 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

  2. 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...

  3. Total Quality Leadership

    Science.gov (United States)

    1991-01-01

    More than 750 NASA, government, contractor, and academic representatives attended the Seventh Annual NASA/Contractors Conference on Quality and Productivity. The panel presentations and Keynote speeches revolving around the theme of total quality leadership provided a solid base of understanding of the importance, benefits, and principles of total quality management (TQM). The presentations from the conference are summarized.

  4. 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

  5. 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.

  6. 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

  7. 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.

  8. Estonian total ozone climatology

    Directory of Open Access Journals (Sweden)

    K. Eerme

    Full Text Available The climatological characteristics of total ozone over Estonia based on the Total Ozone Mapping Spectrometer (TOMS data are discussed. The mean annual cycle during 1979–2000 for the site at 58.3° N and 26.5° E is compiled. The available ground-level data interpolated before TOMS, have been used for trend detection. During the last two decades, the quasi-biennial oscillation (QBO corrected systematic decrease of total ozone from February–April was 3 ± 2.6% per decade. Before 1980, a spring decrease was not detectable. No decreasing trend was found in either the late autumn ozone minimum or in the summer total ozone. The QBO related signal in the spring total ozone has an amplitude of ± 20 DU and phase lag of 20 months. Between 1987–1992, the lagged covariance between the Singapore wind and the studied total ozone was weak. The spring (April–May and summer (June–August total ozone have the best correlation (coefficient 0.7 in the yearly cycle. The correlation between the May and August total ozone is higher than the one between the other summer months. Seasonal power spectra of the total ozone variance show preferred periods with an over 95% significance level. Since 1986, during the winter/spring, the contribution period of 32 days prevails instead of the earlier dominating 26 days. The spectral densities of the periods from 4 days to 2 weeks exhibit high interannual variability.

    Key words. Atmospheric composition and structure (middle atmosphere – composition and chemistry; volcanic effects – Meteorology and atmospheric dynamics (climatology

  9. 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 ...

  10. Total Water Management - slides

    Science.gov (United States)

    Total Water Management (TWM) examines urban water systems in an interconnected manner. It encompasses reducing water demands, increasing water recycling and reuse, creating water supply assets from stormwater management, matching water quality to end-use needs, and achieving envi...

  11. 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 ...

  12. 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 ...

  13. 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. ...

  14. 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 ...

  15. 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.)

  16. 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 ...

  17. 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. ...

  18. 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...

  19. 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 ...

  20. 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 ...

  1. 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 ...

  2. 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 ...

  3. 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.)

  4. Total lymphoid irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Sutherland, D.E.; Ferguson, R.M.; Simmons, R.L.; Kim, T.H.; Slavin, S.; Najarian, J.S.

    1983-05-01

    Total lymphoid irradiation by itself can produce sufficient immunosuppression to prolong the survival of a variety of organ allografts in experimental animals. The degree of prolongation is dose-dependent and is limited by the toxicity that occurs with higher doses. Total lymphoid irradiation is more effective before transplantation than after, but when used after transplantation can be combined with pharmacologic immunosuppression to achieve a positive effect. In some animal models, total lymphoid irradiation induces an environment in which fully allogeneic bone marrow will engraft and induce permanent chimerism in the recipients who are then tolerant to organ allografts from the donor strain. If total lymphoid irradiation is ever to have clinical applicability on a large scale, it would seem that it would have to be under circumstances in which tolerance can be induced. However, in some animal models graft-versus-host disease occurs following bone marrow transplantation, and methods to obviate its occurrence probably will be needed if this approach is to be applied clinically. In recent years, patient and graft survival rates in renal allograft recipients treated with conventional immunosuppression have improved considerably, and thus the impetus to utilize total lymphoid irradiation for its immunosuppressive effect alone is less compelling. The future of total lymphoid irradiation probably lies in devising protocols in which maintenance immunosuppression can be eliminated, or nearly eliminated, altogether. Such protocols are effective in rodents. Whether they can be applied to clinical transplantation remains to be seen.

  5. Algebraic totality, towards completeness

    CERN Document Server

    Tasson, Christine

    2009-01-01

    Finiteness spaces constitute a categorical model of Linear Logic (LL) whose objects can be seen as linearly topologised spaces, (a class of topological vector spaces introduced by Lefschetz in 1942) and morphisms as continuous linear maps. First, we recall definitions of finiteness spaces and describe their basic properties deduced from the general theory of linearly topologised spaces. Then we give an interpretation of LL based on linear algebra. Second, thanks to separation properties, we can introduce an algebraic notion of totality candidate in the framework of linearly topologised spaces: a totality candidate is a closed affine subspace which does not contain 0. We show that finiteness spaces with totality candidates constitute a model of classical LL. Finally, we give a barycentric simply typed lambda-calculus, with booleans ${\\mathcal{B}}$ and a conditional operator, which can be interpreted in this model. We prove completeness at type ${\\mathcal{B}}^n\\to{\\mathcal{B}}$ for every n by an algebraic metho...

  6. 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.

  7. Total versus subtotal hysterectomy

    DEFF Research Database (Denmark)

    Gimbel, Helga; Zobbe, Vibeke; Andersen, Anna Birthe;

    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...... women chose total and 105 women chose subtotal abdominal hysterectomy. No significant differences were found between the 2 operation methods in any of the outcome measures at 12 months. Fourteen women (15%) from the subtotal abdominal hysterectomy group experienced vaginal bleeding and three women had...

  8. Strictness and Totality Analysis

    DEFF Research Database (Denmark)

    Solberg, K. L.; Nielson, Hanne Riis; Nielson, Flemming

    1998-01-01

    We define a novel inference system for strictness and totality analysis for the simply-typed lazy lambda-calculus with constants and fixpoints. Strictness information identifies those terms that definitely denote bottom (i.e. do not evaluate to WHNF) whereas totality information identifies those...... terms that definitely do not denote bottom (i.e. do evaluate to WHNF). The analysis is presented as an annotated type system allowing conjunctions at ?top-level? only. We give examples of its use and prove the correctness with respect to a natural-style operational semantics....

  9. Total hip arthroplasty

    Directory of Open Access Journals (Sweden)

    Slavković Nemanja

    2012-01-01

    Full Text Available Total hip arthroplasty is most common reconstructive hip procedure in adults. In this surgery we replace some parts of the upper femur and acetabulum with biocompatible materials. The main goal of this surgery is to eliminate pain and regain full extent of joint motion, maintaining hip stability. Surgical technique, biomaterials, design of the prosthesis and fixation techniques have evolved with time adjusting to each other. After total hip arthroplasty patients’ quality of life should be improved. There are many various postoperative complications. Some of them are fatal, and some are minor, which may become manifested years after surgery. Each next surgical procedure following previous hip surgery is associated with considerably lower chances to be successful. Therefore, in primary total hip arthroplasty, preoperative evaluation and preparation of patients are essential. Every orthopaedic surgeon needs to improve already adopted surgical skills applying them with precision and without compromise, with the main goal to achieve long-term durability of the selected implant. The number of total hip arthroplasties will also increase in future, and newer and higher quality materials will be used.

  10. 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...

  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. 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 = ...

  13. Total Synthesis of Naloxone

    Institute of Scientific and Technical Information of China (English)

    HU Wen-Xiang; WANG Jian-Ying; XU Ming

    2003-01-01

    @@ Naloxone (1) is one of the 14-hydroxyl substituted opium antagonists which are valuable medications for treat ment of opiate abuse, opiate overdose, and alcohol addiction. Here, the total synthesis of naloxone was described. We selected 2,6-dihydroxynaphalene (2) as the starting material.

  14. 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.)

  15. 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 ...

  16. 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…

  17. 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…

  18. 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.

  19. Polarity Sensitive Bioorthogonally Applicable Far-Red Emitting Labels for Postsynthetic Nucleic Acid Labeling by Copper-Catalyzed and Copper-Free Cycloaddition.

    Science.gov (United States)

    Eördögh, Ádám; Steinmeyer, Jeannine; Peewasan, Krisana; Schepers, Ute; Wagenknecht, Hans-Achim; Kele, Péter

    2016-02-17

    Two series of new, water-soluble, membrane-permeable, far-red/NIR emitting benzothiazolium-based fluorescent labels with large Stokes' shifts were synthesized that can be conjugated to alkyne-modified biomolecules through their azide moiety via azide-alkyne cycloaddition. We have used these azide bearing labels to make fluorescent DNA constructs using copper-catalyzed "click" reaction. All dyes showed good or remarkable fluorescence intensity enhancement upon conjugation to DNA. We also investigated the possibility to incorporate the benzocyclooctyne motif through rigid (ethnynyl) or flexible (ethyl) linkers into the DNA, thus enabling copper-free labeling schemes. We observed that there is a marked difference between the two linkers applied in terms of optical properties of the labeled oligonucleotides. We have also tested the in vivo labeling potential of these newly synthesized dyes on HeLa cells previously transfected with cyclooctynylated DNA. Confocal fluorescent images showed that the dyes are all able to cross the membrane and suitable for background-fluorescence free fluorescent tagging of nucleic acids. Moreover, we have observed different accumulation of the two dye series in the endosomal particles, or in the nuclei, respectively. PMID:26786593

  20. 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

  1. 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.

  2. 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.)

  3. 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.)

  4. 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

  5. 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

    2016-08-01

    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.

  6. Cervical Total Disc Arthroplasty

    OpenAIRE

    Basho, Rahul; Hood, Kenneth A.

    2012-01-01

    Symptomatic adjacent segment degeneration of the cervical spine remains problematic for patients and surgeons alike. Despite advances in surgical techniques and instrumentation, the solution remains elusive. Spurred by the success of total joint arthroplasty in hips and knees, surgeons and industry have turned to motion preservation devices in the cervical spine. By preserving motion at the diseased level, the hope is that adjacent segment degeneration can be prevented. Multiple cervical disc...

  7. 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

  8. 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.

  9. 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.

  10. 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...

  11. 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

  12. 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.)

  13. Supravaginal eller total hysterektomi?

    DEFF Research Database (Denmark)

    Edvardsen, L; Madsen, E M

    1994-01-01

    is 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...... carefully after the supravaginal operation in order to secure that subsequent screening actually is taking place. One must have a normal smear and offer a colposcopic examination before the operation. In general the rate of complications after both kind of hysterectomies is low. However, a few new studies...

  14. 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.

  15. 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.)

  16. 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.)

  17. 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.

  18. 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.

  19. Identity and total institution

    Directory of Open Access Journals (Sweden)

    Ljubičić Milana

    2015-01-01

    Full Text Available This paper analyses a psychiatric institution resident’s identity (self- construction processes. Our quest was grounded on constructivist theoretical paradigm that sees identity as a manner a person defines oneself in accordance with offered social repertoire. In other words, the total institution milieu offers limited range of identities to its residents. On the other hand, the latter are not just passive subjects that identity is imposed upon. They are able to use a number of adjustment mechanisms to the knowledge about themselves - ranging from symbolic escape to open resistance against the imposed image about them; to obedience, and we were interested to understand the (supposed complex dynamic of identity (re-building in, so-called, special or forensic patients. In order to understand this process and attempting to discover, besides the manifest also the latent layer of the story about self, the local, or personal, identity understanding was examined.

  20. 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

  1. 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.

  2. 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...

  3. Brønsted acid-promoted azide–olefin [3 + 2] cycloadditions for the preparation of contiguous aminopolyols: The importance of disiloxane ring size to a diastereoselective, bidirectional approach to zwittermicin A

    Directory of Open Access Journals (Sweden)

    Hubert Muchalski

    2010-12-01

    Full Text Available We report the first study of substrate-controlled diastereoselection in a double [3 + 2] dipolar cycloaddition of benzyl azide with α,β-unsaturated imides. Using a strong Brønsted acid (triflic acid to activate the electron deficient imide π-bond, high diastereoselection was observed provided that a 1,1,3,3-tetraisopropoxydisiloxanylidene group (TIPDS is used to restrict the conformation of the central 1,3-anti diol. This development provides a basis for a stereocontrolled approach to the aminopolyol core of (−-zwittermicin A using a bidirectional synthesis strategy.

  4. 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

  5. Total Solar Eclipse 2001

    Science.gov (United States)

    Craig, Nahide; Hawkins, Isabel

    Evaluation and assessments of informal education programs small or large such as science museum traveling exhibits interpretive kiosks hands-on activities and very large public programs have been challenging due to the diverse nature of objectives setups and expected outcomes of these programs. Almost all institutions that develop and present such programs include in their staff evaluation specialists. However for very large public outreach efforts which include participation of multi institutions located across the country larger evaluation groups/institutions can contribute more objective and extensive evaluation and assessment instruments that will help to identify weather the program was successful and if the learning objectives were achieved. Total Solar Eclipse 2001 event was participated by approximately 42000 people at museums science centers and Planetaria all over the world. I will share with you the results of an evaluation of this event that was surveyed and reported by an independent evaluation company. I will expand further on the properties of this program that helps to determine weather the program was successful or not including the discussion on how personal interest in the content publicity connectivity to a group educational as well as entertainment value and the challenges of using high technology can define success.

  6. 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....

  7. 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

  8. Rotational total skin and total nodal radiotherapy in mycosis fungoides

    Energy Technology Data Exchange (ETDEWEB)

    Bamberg, M.; Molls, M.; Langrock, J.; Muskalla, K.; Quast, U.

    1987-04-01

    The following report describes our technique of rotational total skin radiotherapy with electrons (TSER). We present stage related treatment results. Furthermore our first experiences with the combination of TSER and total nodal irradiation (TNI) are communicated.

  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. Total Restrained Bondage in Graphs

    Institute of Scientific and Technical Information of China (English)

    Nader JAFARI RAD; Roslan HASNI; Joanna RACZEK; Lutz VOLKMANN

    2013-01-01

    A subset S of vertices of a graph G with no isolated vertex is a total restrained dominating set if every vertex is adjacent to a vertex in S and every vertex in V(G)-S is also adjacent to a vertex in V(G)-S.The total restrained domination number of G is the minimum cardinality of a total restrained dominating set of G.In this paper we initiate the study of total restrained bondage in graphs.The total restrained bondage number in a graph G with no isolated vertex,is the minimum cardinality of a subset of edges E such that G-E has no isolated vertex and the total restrained domination number of G-E is greater than the total restrained domination number of G.We obtain several properties,exact values and bounds for the total restrained bondage number of a graph.

  12. Layer-by-Layer Fabrication of Porphyrin Multilayer Films via Copper(I)-Catalyzed Azide-Alkyne Cycloaddition: Film Properties and Applications in Dye-Sensitized Solar Cells

    Science.gov (United States)

    Palomaki, Peter Karl Bunk

    Solar energy may be the only renewable source of energy available to the human race that could provide the energy we require while at the same time minimizing negative impacts on the planet and population. These characteristics may be instrumental in diminishing the potential for societal conflict. In order for photovoltaic devices to succeed on a global scale, research and development must lead to reduced costs and/or increased efficiency. Dye-Sensitized Solar Cells (DSSCs) are one class of nextgeneration photovoltaic technologies with the potential to realize these goals. Herein, I describe efforts towards developing a new light harvesting array of chromophores assembled on oxide substrates using copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC or ‘click’ chemistry) that could prove useful in improving DSCC performance while maintaining low cost and simple fabrication. Specifically, molecular multilayers of porphyrin-based chromophores have been fabricated via sequential selflimiting CuAAC reactions to generate multilayered light harvesting films. Films of synthetic porphyrins, perylenes, and mixtures of the two are constructed in order to highlight the versatility of this molecular layer-by-layer (LbL) technique. Characterization in the form of electrochemical techniques, UV-Visible spectroscopy, infrared spectroscopy (IR), and water contact angle all indicate that the films are reacting as expected. Film thickness and morphology are investigated using X-ray reflectivity showing that film growth displays a high degree of linearity, while the roughness increases with thickness. Growth angles based on the porphyrin plane are estimated via a comparison of molecular models and experimentally determined thickness measurements. A more finite measurement of growth angle (and as a result the primary bonding mode) is determined by grazing angle IR spectroscopy. Blocking layer studies suggest that the films could be useful as a self-passivating layer in DSSCs to

  13. 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).

  14. Core-double-shell Fe3O4@carbon@poly(In(III)-carboxylate) microspheres: cycloaddition of CO2 and epoxides on coordination polymer shells constituted by imidazolium-derived Al(III)-Salen bifunctional catalysts.

    Science.gov (United States)

    An, Qiao; Li, Zifeng; Graff, Robert; Guo, Jia; Gao, Haifeng; Wang, Changchun

    2015-03-01

    A hydrid microsphere Fe3O4@carbon@poly(In(III)-carboxylate) consisting of a cluster of Fe3O4 nanoparticles as the core, a carbon layer as the inner shell and a porous In(III)-carboxylate coordination polymer as the outer shell was prepared and applied as a recyclable catalyst for the cycloaddition reaction of CO2 and epoxides. Construction of this hybrid microsphere was achieved in the two steps, including (1) the one-pot solvothermal synthesis of Fe3O4@C particles with the abundant carboxylic groups on the carbon surface and (2) the subsequent growth of the outer shell polymers based on the precipitation coordination polymerization. Imidazolium-substituted Salen ligands were synthesized and chelated with the In(III) ions using the terminal carboxylic groups. The coordination polymer shell was formed on the Fe3O4@C particles, and the structures including shell thickness, surface area and porosity could be varied by tuning the feeding ratios of the In(III) ions and the ligands. The optimal structure of the coordination polymers showed a shell thickness of ca. 45 nm with ∼5 nm of mesopore, 174.7 m(2)/g of surface area and 0.2175 cm(3)/g of pore volume. In light of gas uptake capability, catalytic activity and magnetic susceptibility, cycloaddition of CO2 with a series of epoxides were studied by using Al-complexed Fe3O4@C@In(III)-[IL-Salen] microspheres. The results validated that the self-supporting catalytic layer with high surface area was of remarkable advantages, which were attributed from great increment of effective active sites and combination of nucleophilic/electrophilic synergistic property and CO2 uptake capability. Therefore, these hybrid microspheres provided excellent catalytic activity, prominent selectivity to cyclic carbonates and outstanding recyclability with the assistance of an applied magnetic field.

  15. 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.

  16. 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

  17. The total charm cross section

    Energy Technology Data Exchange (ETDEWEB)

    Vogt, R

    2007-09-14

    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 the uncertainty on the total charm cross section is difficult to quantify.

  18. 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

  19. 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...

  20. 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...

  1. 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 ...

  2. 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...

  3. 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 ...

  4. 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

  5. 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.

  6. Reduction of total ownership cost

    OpenAIRE

    Boudreau, Michael; Naegle, Brad R.

    2003-01-01

    Acquisition research (Graduate School of Business & Public Policy) Total Ownership Cost (TOC) is the current 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 has implications for Cost As an Independent Variable (CAIV), cost-per...

  7. 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

  8. 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.)

  9. 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.

  10. 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.    

  11. 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.

  12. 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].

  13. 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. ...

  14. 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 ...

  15. 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 ...

  16. 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 ...

  17. ARTHROFIBROSIS FOLLOWING TOTAL KNEE ARTHROPLASTY

    Directory of Open Access Journals (Sweden)

    Ravi B. Solanki

    2014-11-01

    Full Text Available Arthrofibrosis following total knee arthroplasty is an uncommon complication defined as less than 80 degrees of knee flexion 6-8 weeks post operatively. It is characterized by abnormal scarring of the joint in which the formation of dense fibrous tissue and tissue metaplasia prevent normal range of motion. Clinical features include limited knee Range of motion with extension deficit, pain with activities of daily living and unusual amount of pain and swelling post operatively in the absence of infection, bleeding or mechanical complications. We present case of 55 years old female who undergone for total knee replacement before 3 months and presented to our department with complain of knee pain and swelling with activities of daily living. She was diagnosed on the basis of clinical examination. Her detailed evaluation was carried out and Physiotherapy treatment was started.

  18. Subtotal versus total abdominal hysterectomy

    DEFF Research Database (Denmark)

    Andersen, Lea Laird; Ottesen, Bent; Alling Møller, Lars Mikael;

    2015-01-01

    , constipation, pain, sexuality, quality of life (Short Form-36 questionnaire), hospital contacts, and vaginal bleeding. RESULTS: The questionnaire was answered by 197 of 304 women (64.8%) (subtotal hysterectomy [n = 97] [63.4%]; total hysterectomy [n = 100] [66.2%]). Mean follow-up time was 14 years and mean...... hysterectomy. All women enrolled in the trial from 1996 to 2000 who were still alive and living in Denmark (n = 304) were invited to answer the validated questionnaire used in prior 1 and 5 year follow-ups. Hospital contacts possibly related to hysterectomy from 5 to 14 years postoperatively were registered......, randomized clinical trial without blinding. Eleven gynecological departments in Denmark contributed participants to the trial. Women referred for benign uterine diseases who did not have contraindications to subtotal abdominal hysterectomy were randomized to subtotal (n = 161) vs total (n = 158) abdominal...

  19. 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...

  20. 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.

  1. 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...

  2. 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

  3. Employees in Total Quality Management

    OpenAIRE

    M. G. Matlhape; N. Lessing

    2002-01-01

    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 ...

  4. TOTAL annual report 2003; TOTAL rapport annuel 2003

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2004-07-01

    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.)

  5. Intrathoracic Hernia after Total Gastrectomy

    Directory of Open Access Journals (Sweden)

    Yoshihiko Tashiro

    2016-05-01

    Full Text Available Intrathoracic hernias after total gastrectomy are rare. We report the case of a 78-year-old man who underwent total gastrectomy with antecolic Roux-Y reconstruction for residual gastric cancer. He had alcoholic liver cirrhosis and received radical laparoscopic proximal gastrectomy for gastric cancer 3 years ago. Early gastric cancer in the remnant stomach was found by routine upper gastrointestinal endoscopy. We initially performed endoscopic submucosal dissection, but the vertical margin was positive in a pathological result. We performed total gastrectomy with antecolic Roux-Y reconstruction by laparotomy. For adhesion of the esophageal hiatus, the left chest was connected with the abdominal cavity. A pleural defect was not repaired. Two days after the operation, the patient was suspected of having intrathoracic hernia by chest X-rays. Computed tomography showed that the transverse colon and Roux limb were incarcerated in the left thoracic cavity. He was diagnosed with intrathoracic hernia, and emergency reduction and repair were performed. Operative findings showed that the Roux limb and transverse colon were incarcerated in the thoracic cavity. After reduction, the orifice of the hernia was closed by suturing the crus of the diaphragm with the ligament of the jejunum and omentum. After the second operation, he experienced anastomotic leakage and left pyothorax. Anastomotic leakage was improved with conservative therapy and he was discharged 76 days after the second operation.

  6. Intrathoracic Hernia after Total Gastrectomy.

    Science.gov (United States)

    Tashiro, Yoshihiko; Murakami, Masahiko; Otsuka, Koji; Saito, Kazuhiko; Saito, Akira; Motegi, Kentaro; Date, Hiromi; Yamashita, Takeshi; Ariyoshi, Tomotake; Goto, Satoru; Yamazaki, Kimiyasu; Fujimori, Akira; Watanabe, Makoto; Aoki, Takeshi

    2016-01-01

    Intrathoracic hernias after total gastrectomy are rare. We report the case of a 78-year-old man who underwent total gastrectomy with antecolic Roux-Y reconstruction for residual gastric cancer. He had alcoholic liver cirrhosis and received radical laparoscopic proximal gastrectomy for gastric cancer 3 years ago. Early gastric cancer in the remnant stomach was found by routine upper gastrointestinal endoscopy. We initially performed endoscopic submucosal dissection, but the vertical margin was positive in a pathological result. We performed total gastrectomy with antecolic Roux-Y reconstruction by laparotomy. For adhesion of the esophageal hiatus, the left chest was connected with the abdominal cavity. A pleural defect was not repaired. Two days after the operation, the patient was suspected of having intrathoracic hernia by chest X-rays. Computed tomography showed that the transverse colon and Roux limb were incarcerated in the left thoracic cavity. He was diagnosed with intrathoracic hernia, and emergency reduction and repair were performed. Operative findings showed that the Roux limb and transverse colon were incarcerated in the thoracic cavity. After reduction, the orifice of the hernia was closed by suturing the crus of the diaphragm with the ligament of the jejunum and omentum. After the second operation, he experienced anastomotic leakage and left pyothorax. Anastomotic leakage was improved with conservative therapy and he was discharged 76 days after the second operation. PMID:27403095

  7. A signal-on electrochemical DNA biosensor based on potential-assisted Cu(I)-catalyzed azide-alkyne cycloaddition mediated labeling of hairpin-like oligonucleotide with electroactive probe.

    Science.gov (United States)

    Hu, Qiong; Kong, Jinming; Li, Yajie; Zhang, Xueji

    2016-01-15

    A novel electrochemical biosensor was developed for the signal-on detection of sequence-specific DNA by exploiting potential-assisted Cu(I)-catalyzed azide-alkyne cycloaddition (φCuAAC) as an efficient approach for the labeling of hairpin-like oligonucleotide (hairpin) with electroactive probe. The hairpins, dually labeled with thiol and azide at either terminal, were firstly self-assembled on gold electrode and served as the capture probes for the specific recognition of target DNA. Upon hybridization with target DNA, the surface-confined hairpins were unfolded, liberating the azide-containing terminals away from electrode surface. Subsequently, the unfolded hairpins were conveniently and efficiently labeled with ethynylferrocene (EFC) via the φCuAAC. The quantitatively labeled EFC was finally measured via differential pulse voltammetry (DPV) for the signal-on electrochemical detection of sequence-specific DNA. The biosensor presented a good linear response over the range from 1pM to 1nM with a detection limit of 0.62pM. Results also revealed that it was highly specific and held a good detection capability in serum samples. Furthermore, the ability to chemoselectively label hairpin-like oligonucleotide with signal reporter by electrical addressing, together with the simplicity and efficiency of the φCuAAC, makes it compatible with microfluidic devices and microelectrode arrays to achieve the miniaturized and multiplexed detections.

  8. Total light absorption in graphene

    CERN Document Server

    Thongrattanasiri, Sukosin; de Abajo, F Javier Garcia

    2011-01-01

    We demonstrate that 100% light absorption can take place in a single patterned sheet of doped graphene. General analysis shows that a planar array of small lossy particles exhibits full absorption under critical-coupling conditions provided the cross section of each individual particle is comparable to the area of the lattice unit-cell. Specifically, arrays of doped graphene nanodisks display full absorption when supported on a substrate under total internal reflection, and also when lying on a dielectric layer coating a metal. Our results are relevant for infrared light detectors and sources, which can be made tunable via electrostatic doping of graphene.

  9. 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

  10. 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

  11. 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.

  12. The total synthesis of (-)-nitidasin.

    Science.gov (United States)

    Hog, Daniel T; Huber, Florian M E; Mayer, Peter; Trauner, Dirk

    2014-08-01

    Nitidasin is a pentacyclic sesterterpenoid with a rare 5-8-6-5 carbon skeleton that was isolated from the Peruvian folk medicine "Hercampuri". It belongs to a small class of sesterterpenoids that feature an isopropyl trans-hydrindane moiety fused to a variety of other ring systems. As a first installment of our general approach toward these natural products, we report the total synthesis of the title compound. Our stereoselective, convergent route involves the addition of a complex alkenyl lithium compound to a trans-hydrindanone, followed by chemoselective epoxidation, ring-closing olefin metathesis, and redox adjustment.

  13. 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.

  14. 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)

  15. 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

  16. 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.

  17. 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.

  18. TOTAL LAPAROSCOPIC HYSTERECTOMY VERSUS TOTAL ABDOMINAL HYSTERECTOMY: A RETROSPECTIVE STUDY

    Directory of Open Access Journals (Sweden)

    Virupaksha

    2015-10-01

    Full Text Available BACKGROUND: Hysterectomy is a common gynaecological surgery which can be done by abdominal, vaginal or laparoscopic routes or with robotic assistance. Although there were concerns regarding the safety of laparoscopic surgery, a newer technique when compared with abdominal hysterectomy, it is now being reco gnized as a safe procedure in the hands of an experienced surgeon. AIMS: This study was done to compare the intra - operative and post - operative parameters of abdominal and laparoscopic hysterectomy. SETTINGS AND DESIGN: This study was done at JSS Hospital, Mysore between June 2013 and September 2014. It is a retrospective study . MATERIALS AND METHOD S: Patients admitted in the Department of Obstetrics and Gynaecology at JSS Hospital, JSS University, Mysore, with an indication for total abdominal hysterectomy( TAH or total laparoscopic hysterectomy(TLH for benign pathology from June 2013 to September 2014 were included in the study. Exclusion criteria were suspicion of malignancy, vaginal prolapse higher than first degree and those undergoing laparoscopic assi sted vaginal hysterectomy. Baseline characteristics, intraoperative and postoperative parameters were compared between the two groups. STATISTICAL ANALYSIS : The data were analyzed using independent T test, Chi square test and Mann Whitney test. A p value o f <0 . 05 was accepted as significant. RESULTS: The mean time taken to perform TLH was significantly longer, i.e. 113.46 minutes compared with TAH, i.e. 70.44 minutes, with the p value being <0.0001. But the duration of stay in the hospital was shorter for t he women undergoing TLH, mean duration being 3.74 days as opposed to 7.65 days in women undergoing TAH. This difference was also statistically significant with p value being <0.0001. Also, women undergoing TAH required more analgesic doses (mean 3.29 than those undergoing TLH (mean 1.36 and this difference was also statistically significant. CONCLUSION: Although TLH took a

  19. 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

  20. TVD: Total Variation Diminishing code

    Science.gov (United States)

    Pen, Ue-Li; Arras, Phil; Wong, ShingKwong

    2013-04-01

    TVD solves the magnetohydrodynamic (MHD) equations by updating the fluid variables along each direction using the flux-conservative, second-order, total variation diminishing (TVD), upwind scheme of Jin & Xin. The magnetic field is updated separately in two-dimensional advection-constraint steps. The electromotive force (EMF) is computed in the advection step using the TVD scheme, and this same EMF is used immediately in the constraint step in order to preserve \\Downtriangle B=0 without the need to store intermediate fluxes. The code is extended to three dimensions using operator splitting, and Runge-Kutta is used to get second-order accuracy in time. TVD offers high-resolution per grid cell, second-order accuracy in space and time, and enforcement of the \\Downtriangle B=0 constraint to machine precision. Written in Fortran, It has no memory overhead and is fast. It is also available in a fully scalable message-passing parallel MPI implementation.

  1. 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.

  2. 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.

  3. 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)

  4. 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

  5. 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.

  6. Stiffness after total knee arthroplasty.

    Science.gov (United States)

    Manrique, Jorge; Gomez, Miguel M; Parvizi, Javad

    2015-04-01

    Stiffness after total knee arthroplasty (TKA) adversely affects outcome and impacts patient function. Various risk factors for stiffness after TKA have been identified, including reduced preoperative knee range of motion, history of prior knee surgery, etiology of arthritis, incorrect positioning or oversizing of components, and incorrect gap balancing. Mechanical and associated causes, such as infection, arthrofibrosis, complex regional pain syndrome, and heterotopic ossification, secondary gain issues have also been identified. Management of stiffness following TKA can be challenging. The condition needs to be assessed and treated in a staged manner. A nonsurgical approach is the first step. Manipulation under anesthesia may be considered within the first 3 months after the index TKA, if physical therapy fails to improve the range of motion. Beyond this point, consideration should be given to surgical intervention such as lysis of adhesions, either arthroscopically or by open arthrotomy. If the cause of stiffness is deemed to be surgical error, such as component malpositioning, revision arthroplasty is indicated. The purpose of this article is to evaluate the various aspects of management of stiffness after TKA.

  7. Stiffness after total knee arthroplasty.

    Science.gov (United States)

    Manrique, Jorge; Gomez, Miguel M; Parvizi, Javad

    2015-04-01

    Stiffness after total knee arthroplasty (TKA) adversely affects outcome and impacts patient function. Various risk factors for stiffness after TKA have been identified, including reduced preoperative knee range of motion, history of prior knee surgery, etiology of arthritis, incorrect positioning or oversizing of components, and incorrect gap balancing. Mechanical and associated causes, such as infection, arthrofibrosis, complex regional pain syndrome, and heterotopic ossification, secondary gain issues have also been identified. Management of stiffness following TKA can be challenging. The condition needs to be assessed and treated in a staged manner. A nonsurgical approach is the first step. Manipulation under anesthesia may be considered within the first 3 months after the index TKA, if physical therapy fails to improve the range of motion. Beyond this point, consideration should be given to surgical intervention such as lysis of adhesions, either arthroscopically or by open arthrotomy. If the cause of stiffness is deemed to be surgical error, such as component malpositioning, revision arthroplasty is indicated. The purpose of this article is to evaluate the various aspects of management of stiffness after TKA. PMID:25513992

  8. 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 ...

  9. Total joint replacement preadmission programs.

    Science.gov (United States)

    Messer, B

    1998-01-01

    Patients begin to formulate their expectations of the postoperative hospitalization during the preadmission program. The challenge is to better understand the factors patients consider when formulating judgments about the quality of preadmission education. For example, it may be that perceptions of the preadmission program are influenced by what patients believe about their postoperative pain and functional abilities. Specific attention needs to be given both preoperatively and postoperatively to instructing patients on realistic expectations for recovery. One other method of measuring patient outcomes is with the Health Status Profile (SF-36) (Response Healthcare Information Management, 1995). The SF-36 approach emphasizes the outcome of medical care as the patient sees it, in addition to a clinical evaluation of successful health care. This form is currently initiated in the physician's office and returned for scanning at the preadmission class. The patient then completes another SF-36 at 6 months and every year thereafter to compare measurable outcomes. Patients intending to have elective total joint replacements experience anxiety and require much support and education. An effective preadmission program is a major investment in a patient's recovery, as well as a unique marketing tool to customers. Preadmission programs can be viewed as an opportunity to enhance customer satisfaction. Preadmission clinics are an excellent means for nurses to improve the quality of patient care through patient education. the overall goal of preadmission testing programs is to ensure patient preparedness while increasing quality health care and overall customer satisfaction. To enhance program effectiveness, health care providers must lead collaborative efforts to improve the efficiency of systems. PMID:9601410

  10. Total joint replacement preadmission programs.

    Science.gov (United States)

    Messer, B

    1998-01-01

    Patients begin to formulate their expectations of the postoperative hospitalization during the preadmission program. The challenge is to better understand the factors patients consider when formulating judgments about the quality of preadmission education. For example, it may be that perceptions of the preadmission program are influenced by what patients believe about their postoperative pain and functional abilities. Specific attention needs to be given both preoperatively and postoperatively to instructing patients on realistic expectations for recovery. One other method of measuring patient outcomes is with the Health Status Profile (SF-36) (Response Healthcare Information Management, 1995). The SF-36 approach emphasizes the outcome of medical care as the patient sees it, in addition to a clinical evaluation of successful health care. This form is currently initiated in the physician's office and returned for scanning at the preadmission class. The patient then completes another SF-36 at 6 months and every year thereafter to compare measurable outcomes. Patients intending to have elective total joint replacements experience anxiety and require much support and education. An effective preadmission program is a major investment in a patient's recovery, as well as a unique marketing tool to customers. Preadmission programs can be viewed as an opportunity to enhance customer satisfaction. Preadmission clinics are an excellent means for nurses to improve the quality of patient care through patient education. the overall goal of preadmission testing programs is to ensure patient preparedness while increasing quality health care and overall customer satisfaction. To enhance program effectiveness, health care providers must lead collaborative efforts to improve the efficiency of systems.

  11. 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 ...

  12. Evolution of the total logistics costs concept

    Directory of Open Access Journals (Sweden)

    2011-09-01

    Full Text Available The article considers the evolution stages of the total logistics cost concept; an interrelations of TLC and EOQ models has been analyzed. The author presented analytical approaches to determine a value of total cost, as well as an integral criterion for logistics systems' functioning, based upon package treatment of the total costs value and service level.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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...

  18. 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....

  19. 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.

  20. 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

  1. 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.

  2. (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_...

  3. The total bondage number of grid graphs

    CERN Document Server

    Hu, Fu-Tao; Xu, Jun-Ming

    2011-01-01

    The total domination number of a graph $G$ without isolated vertices is the minimum number of vertices that dominate all vertices in $G$. The total bondage number $b_t(G)$ of $G$ is the minimum number of edges whose removal enlarges the total domination number. This paper considers grid graphs. An $(n,m)$-grid graph $G_{n,m}$ is defined as the cartesian product of two paths $P_n$ and $P_m$. This paper determines the exact values of $b_t(G_{n,2})$ and $b_t(G_{n,3})$, and establishes some upper bounds of $b_t(G_{n,4})$.

  4. 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.

  5. 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.

  6. 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 ...

  7. 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.

  8. 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.

  9. 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...

  10. 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...

  11. 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...

  12. ROE Total Sulfur Deposition 2011-2013

    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 2011 to 2013 at a set of point locations across the...

  13. 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.

  14. Non-blocking message total ordering protocol

    Institute of Scientific and Technical Information of China (English)

    WANG Yun; WANG JunLing

    2008-01-01

    Message total ordering is a critical part in active replication in order to maintain consistency among members in a fault tolerant group. The paper proposes a non-blocking message total ordering protocol (NBTOP) for distributed systems. Non-blocking property refers to that the members in a fault tolerant group keep on running independently without waiting for installing the same group view when a fault tolerant group evolves even when decision messages collide. NBTOP takes advantage of token ring as its logical control way. Members adopt re-requesting mechanism (RR) to obtain their lost decisions. Forward acknowledgement mechanism (FA) is put forth to solve decision collisions. The paper further proves that NBTOP satisfies the properties of total order, agreement, and termination. NBTOP is implemented, and its performance test is done. Comparing with the performance of Totem, the results show that NBTOP has a better total ordering delay. It manifests that non-blocking property helps to improve protocol efficiency.

  15. 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.

  16. 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 ...

  17. 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...

  18. 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)

  19. 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...

  20. Total ankle replacement - surgical treatment and rehabilitation.

    Science.gov (United States)

    Prusinowska, Agnieszka; Krogulec, Zbigniew; Turski, Piotr; Przepiórski, Emil; Małdyk, Paweł; Księżopolska-Orłowska, Krystyna

    2015-01-01

    Functions of the ankle joint are closely connected with the gait and ability to maintain an upright position. Degenerative lesions of the joint directly contribute to postural disorders and greatly restrict propulsion of the foot, thus leading to abnormal gait. Development of total ankle replacement is connected with the use of the method as an efficient treatment of joint injuries and continuation of achievements in hip and knee surgery. The total ankle replacement technique was introduced as an alternative to arthrodesis, i.e. surgical fixation, which made it possible to preserve joint mobility and to improve gait. Total ankle replacement is indicated in post-traumatic degenerative joint disease and joint destruction secondary to rheumatoid arthritis. In this paper, total ankle replacement and various types of currently used endoprostheses are discussed. The authors also describe principles of early postoperative rehabilitation as well as rehabilitation in the outpatient setting.

  1. Stereoselective Total Synthesis of (-)-Renieramycin T.

    Science.gov (United States)

    Yokoya, Masashi; Toyoshima, Ryoko; Suzuki, Toshihiro; Le, Vy H; Williams, Robert M; Saito, Naoki

    2016-05-20

    A stereoselective total synthesis of (-)-Renieramycin T (1t) from a key tetrahydroisoquinoline intermediate previously utilized in our formal total synthesis of Ecteinascidin 743 is described. The synthesis features a concise approach for construction of the pentacyclic framework using a Pictet-Spengler cyclization of bromo-substituted carbinolamine 17, which obviates the regioselectivity problem of the Pictet-Spengler cyclization. The results of cytotoxicity studies are also presented. PMID:27019081

  2. 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...

  3. 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.)

  4. 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...

  5. 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...

  6. 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-...

  7. Total Sleep Time Severely Drops during Adolescence

    OpenAIRE

    Damien Leger; François Beck; Jean-Baptiste Richard; Emmanuelle Godeau

    2012-01-01

    UNLABELLED: Restricted sleep duration among young adults and adolescents has been shown to increase the risk of morbidities such as obesity, diabetes or accidents. However there are few epidemiological studies on normal total sleep time (TST) in representative groups of teen-agers which allow to get normative data. PURPOSE: To explore perceived total sleep time on schooldays (TSTS) and non schooldays (TSTN) and the prevalence of sleep initiating insomnia among a nationally representative samp...

  8. 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...

  9. 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 ...

  10. 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...

  11. 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...

  12. Total OH reactivity emissions from Norway spruce

    Science.gov (United States)

    Nölscher, Anke; Bourtsoukidis, Efstratios; Bonn, Boris; Kesselmeier, Jürgen; Lelieveld, Jos; Williams, Jonathan

    2013-04-01

    Forest emissions represent a strong potential sink for the main tropospheric oxidant, the hydroxyl radical (OH). In forested environments, the comparison of the directly determined overall sink of OH radicals, the total OH reactivity, and the individually measured OH sink compounds often exposes a significant gap. This "missing" OH reactivity can be high and influenced by both direct biogenic emissions and secondary photo-oxidation products. To investigate the source of the missing OH sinks in forests, total OH reactivity emission rates were determined for the first time from a Norway spruce (Picea abies) throughout spring, summer and autumn 2011. The total OH reactivity was measured inside a branch enclosure using the Comparative Reactivity Method (CRM) with a Proton Transfer Reaction-Mass Spectrometer (PTR-MS) as the detector. In parallel, separate volatile organic compounds (VOC) emission rates were monitored by a second PTR-MS, including the signal of isoprene, acetaldehyde, total monoterpenes and total sesquiterpenes. The comparison of known and PTR-MS detected OH sink compounds and the directly measured total OH reactivity emitted from Norway spruce revealed unmeasured and possibly unknown primary biogenic emissions. These were found to be highest in late summer during daytime coincident with highest temperatures and ozone levels.

  13. Solution to causality paradox upon total reflection

    Institute of Scientific and Technical Information of China (English)

    LIU Xiang-min; CAO Zhuang-qi; ZHU Peng-fei; SHEN Qi-shun

    2006-01-01

    A dispute about the existence of an additional time (named as the Goos-H(a)nchen time) associated with the Goos-H(a)nchen shift in total reflection has recently arisen.At the same time,an inconsistency between the optical ray model and the electromagnetic theory also appears in the optical planar waveguide.By analyzing light propagation in an optical planar waveguide with both the zigzag-ray model and the electromagnetic theory,this paper shows that the Goos-H(a)nchen time really exists,and the total time delay upon total reflection upon an ideal nonabsorbing plasma mirror is the sum of the group-delay time and the Goos-H(a)nchen time.The causality paradox of total reflection of a TM wave upon an ideal nonabsorbing plasma mirror is also solved taking into consideration the negative Goos-H(a)nchen shift.Finally,the expression of the group velocity of the guided mode in optical planar waveguide was obtained,which clearly shows that the time delay upon total reflection is the sum of the group-delay time and the Goos-H(a)nchen time at given any time.

  14. 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 patients......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...... 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....

  15. Primary total hip arthroplasty for acetabular fracture

    Institute of Scientific and Technical Information of China (English)

    WANG Zi-ming; SUN Hong-zhen; WANG Ai-min; DU Quan-yin; WU Siyu; ZHAO Yu-feng; TANG Ying

    2006-01-01

    Objective: To explore the operative indications and operative methods of primary total hip arthroplasty for acetabular fracture and to observe the clinical curative effect.Methods: We retrospectively summarized and analyzed the traumatic conditions, fracture types, complications,operative time, operative techniques, and short-term curative effect of 11 patients( 10 males and 1 female, with a mean age of 42. 4 years ) with acetabular fracture who underwent primary total hip arthroplasty.Results: The patients were followed up for 6-45 months ( mean = 28 months). Their average Harris score of postoperative hip joint was 78.Conclusion: Under strict mastery of indications,patients with acetabular fracture may undergo primary total hip arthroplasty, but stable acetabular components should be made.

  16. 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

  17. Totally Corrective Boosting for Regularized Risk Minimization

    CERN Document Server

    Shen, Chunhua; Barnes, Nick

    2010-01-01

    Consideration of the primal and dual problems together leads to important new insights into the characteristics of boosting algorithms. In this work, we propose a general framework that can be used to design new boosting algorithms. A wide variety of machine learning problems essentially minimize a regularized risk functional. We show that the proposed boosting framework, termed CGBoost, can accommodate various loss functions and different regularizers in a totally-corrective optimization fashion. We show that, by solving the primal rather than the dual, a large body of totally-corrective boosting algorithms can actually be efficiently solved and no sophisticated convex optimization solvers are needed. We also demonstrate that some boosting algorithms like AdaBoost can be interpreted in our framework--even their optimization is not totally corrective. We empirically show that various boosting algorithms based on the proposed framework perform similarly on the UCIrvine machine learning datasets [1] that we hav...

  18. 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.

  19. 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.)

  20. 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.

  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. 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...

  5. 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...

  6. 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.

  7. Total Internal Reflection and the Related Effects

    CERN Document Server

    Kristoffel, Nikolai

    2014-01-01

    This submission presents the English translation of the early paper by N.Kristoffel appeared in Russian in the Proceedings 0f the Tartu State University No 42 p.94-112, 1956. It reflects the work done in Tartu State University (Estonia)1n 1950-s on the total internal reflection and associated effects. This paper can be of interest for the scientific community because it remained not well known during the long period. The conceptual paper of N.Kristoffel mentioned includes as the central result the prediction of the transversal shift of the totally reflected light beam.

  8. 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 ...

  9. [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

  10. The technology behind Colgate Total Advanced Fresh.

    Science.gov (United States)

    Williams, Malcolm I; Cummins, Diane

    2003-09-01

    In the early 1990s, a breakthrough toothpaste, Colgate Total, was launched with documented long-lasting activity against plaque, gingivitis, calculus, tooth decay, and bad breath. The technology behind this toothpaste is the combination of triclosan, a polyvinylmethylether/maleic acid copolymer, and sodium fluoride. The copolymer ensures maximal oral retention and subsequent release of the antibacterial triclosan. Effective levels of triclosan have been observed in the oral cavity 12 hours after brushing the teeth, allowing prolonged control of oral bacteria that may cause the most common dental problems, including bad breath. Similarly, the enhanced retention of triclosan to oral surfaces after using this revolutionary toothpaste for up to 2 years has led to significantly reduced incremental coronal caries compared to an American Dental Association-Approved anticavity fluoride toothpaste. Furthermore, significantly less calcium remained in dental plaque after brushing the teeth with the triclosan/copolymer toothpaste, resulting in the formation of less tartar. In keeping with the multiple oral health benefits provided by Colgate Total, consumers are now offered a new dentifrice, Colgate Total Advanced Fresh, which provides the numerous therapeutic and esthetic benefits that are the hallmark of Colgate Total. The new dentifrice, which contains an impactful breath-freshening flavor, has been documented to provide sustained control of bad breath over 12 hours.

  11. Asymmetric Total Synthesis of (-)-Cladospolide B

    Institute of Scientific and Technical Information of China (English)

    WANG,Wen-Kuan; ZHANG,Ji-Yong; HE,Jin-Mei; TANG,Shi-Bing; WANG,Xiao-Lei; SHE,Xue-Gong; PAN,Xin-Fu

    2008-01-01

    An enantioselective total synthesis of (-)-cladospolide B was described.The key steps in this synthesis include (a) a Sharpless asymmetric dihydroxylation to elaborate syn diol at C-4 and C-5 positions;(b) a Mitsunobu esterification to reverse the configuration at C-11 from (S) to (R);and (c) a ring-closing metathesis to access the 12-membered macrocyclic ring.

  12. 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

  13. 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-o...

  14. 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…

  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. Total synthesis: Towards artificial terpene cyclases

    Science.gov (United States)

    Willot, Matthieu; Christmann, Mathias

    2010-07-01

    The plant-derived sesquiterpene englerin A is a potent inhibitor of several renal cancer cell lines. Two recent total syntheses have utilized cationic gold(I)-complexes to coax readily available open-chain precursors into englerin's challenging oxotricyclic core with enzyme-like precision.

  17. 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.

  18. Learning Language through Total Physical Response.

    Science.gov (United States)

    Marlatt, Edward A.

    1995-01-01

    The Total Physical Response (TPR) method of language instruction is introduced, and guidelines for designing and implementing TPR lessons for students with hearing impairments are provided. In TPR instruction, students develop understanding before speech or signing, understanding is demonstrated through actions, and new vocabulary is developed…

  19. 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

  20. 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

  1. 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

  2. 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.

  3. 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.

  4. A formal model for total quality management

    NARCIS (Netherlands)

    S.C. van der Made-Potuijt; H.B. Bertsch (Boudewijn); L.P.J. Groenewegen

    1996-01-01

    textabstractTotal Quality Management (TQM) is a systematic approach to managing a company. TQM is systematic in the sense that it is uses facts through observation, analysis and measurable goals. There are theoretical descriptions of this management concept, but there is no formal model of it. A for

  5. Total Quality Management (TQM) in Higher Education.

    Science.gov (United States)

    Sullivan, Michael F.

    This document consists largely of paper versions of the transparencies used by the author to give his conference paper on Total Quality Management (TQM) in the college and university setting. An introduction lists a series of definitional phrases, a list of what TQM is not, and 11 fundamental principles describing what TQM is. The three major…

  6. PROCEDURE FOR ESTIMATING PERMANENT TOTAL ENCLOSURE COSTS

    Science.gov (United States)

    The paper discusses a procedure for estimating permanent total enclosure (PTE) costs. (NOTE: Industries that use add-on control devices must adequately capture emissions before delivering them to the control device. One way to capture emissions is to use PTEs, enclosures that mee...

  7. Sir John Charnley en de totale heuparthroplastiek

    NARCIS (Netherlands)

    P.T.P.W. Burgers (Paul T. P. W.); J. van Gijn (Jan)

    2011-01-01

    textabstractJohn Charnley, grondlegger van de moderne totale heuparthroplastiek, wordt in 1911 geboren in Bury (Lancashire). Zijn vader, Arthur, is chemicus in het nabijgelegen Manchester en zijn moeder, Lily, verpleegkundige in het Crumpsall Hospital. In 1929 start Charnley de opleiding geneeskunde

  8. 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

  9. 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 …

  10. 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

  11. Favorable results after total wrist arthroplasty

    DEFF Research Database (Denmark)

    Boeckstyns, Michel E. H.; Herzberg, G.; Merser, Søren

    2013-01-01

    Background and purpose During the past 40 years, several attempts have been made with total wrist arthroplasty to avoid fusion in severely destroyed wrists. The results have often been disappointing. There is only modest clinical documentation due to the small number of patients (especially non-r...

  12. 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).

  13. Applying Total Quality Management to Business Education.

    Science.gov (United States)

    Brown, Daniel J.; Koenig, Harold F.

    1993-01-01

    Responses from 390 business school alumni (60%) show that students want educators to consider their opinions about their overall educational experience and what happens after graduation. A total quality management approach can help discover customer/student needs, establish a focus on improvement, and implement a process orientation. (SK)

  14. Total Synthesis of (±)-Celaphanol A

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The first total synthesis of (±)-Celaphanol A was accomplished starting from α-cyclocitral and 3,4-dimethoxy benzyl chloride via a six-step process, in which the intramolecular cyclization of ketone 4 with BF3@Et2O afforded an all-cis isomer intermediate for synthesis of aromatic tricyclic diterpenes.

  15. Total pancreatic lipomatosis with malabsorption syndrome

    Directory of Open Access Journals (Sweden)

    Rama Anand

    2011-01-01

    Full Text Available Total fat replacement of the pancreas is rare. Focal fatty replacement is the most common degenerative lesion of pancreas. Focal fatty deposits have no major clinical significance; however, extreme fat replacement is of pathologic significance, as it is associated with marked reduction in exocrine function of pancreas, resulting in malabsorption due to pancreatic enzyme insufficiency.

  16. Crossing Total Occlusions: Navigating Towards Recanalization

    NARCIS (Netherlands)

    A. Sakes (Aimée); E.S. Regar (Eveline); J. Dankelman (Jenny); P. Breedveld (Paul)

    2016-01-01

    textabstractChronic total occlusions (CTOs) represent the “last frontier” of percutaneous interventions. The main technical challenges lies in crossing the guidewire into the distal true lumen, which is primarily due to three problems: device buckling during initial puncture, inadequate visualizatio

  17. Crossing Total Occlusions: Navigating Towards Recanalization

    NARCIS (Netherlands)

    Sakes, A.; Regar, E.; Dankelman, J; Breedveld, P.

    2016-01-01

    Chronic total occlusions (CTOs) represent the “last frontier” of percutaneous interventions. The main technical challenges lies in crossing the guidewire into the distal true lumen, which is primarily due to three problems: device buckling during initial puncture, inadequate visualization, and the i

  18. 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

  19. 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. ...

  20. 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...

  1. 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

  2. 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

  3. 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

  4. Food safety and total quality management

    NARCIS (Netherlands)

    Barendsz, A.W.

    1998-01-01

    Food safety is a growing global concern not only because of its continuing importance for public health but also because of its impact on international trade. The application of total quality management (TQM) provides the best possible care by continuously improving products and services to meet or

  5. 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.

  6. Total synthesis of aeruginosin 98B.

    Science.gov (United States)

    Trost, Barry M; Kaneko, Toshiyuki; Andersen, Neil G; Tappertzhofen, Christoph; Fahr, Bruce

    2012-11-21

    The first total synthesis of aeruginosin 98B was accomplished. The key step is a highly diastereoselective Pd-catalyzed intramolecular asymmetric allylic alkylation reaction of a diastereomeric mixture of allylic carbonates that is enabled by the use of racemic phosphine ligand L1.

  7. 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.

  8. 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. ...

  9. 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.

  10. 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

  11. 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。

  12. 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)

  13. 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.)

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. Totally Laparoscopic Gastrectomy for Gastric Cancer

    OpenAIRE

    Theodorous, Arianne N.; Train, William W.; Goldfarb, Michael A.; Borao, Frank J.

    2013-01-01

    Background and Objectives: Recent studies have supported minimally invasive techniques as a viable alternative to open surgery in the treatment of gastric cancer. The goal of this study is to review our institution's experience with totally laparoscopic gastrectomy for the treatment of both early- and advanced-stage gastric cancer. Methods: A retrospective study was conducted to examine the short-term outcomes of laparoscopic gastrectomy performed at Monmouth Medical Center between May 2003 a...

  1. Infected total knee arthroplasty treatment outcome analysis

    OpenAIRE

    Radoičić Dragan; Popović Zoran; Barjaktarović Radoslav; Marinković Jugoslav

    2012-01-01

    Background/Aim. Infected total knee arthroplasty (TKA) is a topic of great importance, because its diagnosing and treatment requires a lot of resources, and often has an unsatisfactory outcome. The aim of this study was to analyze the outcome of the treatment of infection developed following TKA. Methods. This retrospective study of infected TKAs was performed in the period from 1998 to 2008 in the Orthopedics & Traumatology Clinic of the Military Medical Academy (MMA) in Belgrade. ...

  2. NASA total quality management 1990 accomplishments report

    Science.gov (United States)

    1991-01-01

    NASA's efforts in Total Quality Management are based on continuous improvement and serve as a foundation for NASA's present and future endeavors. Given here are numerous examples of quality strategies that have proven effective and efficient in a time when cost reduction is critical. These accomplishment benefit our Agency and help to achieve our primary goal, keeping American in the forefront of the aerospace industry.

  3. 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.)

  4. 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. ...

  5. 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

  6. Total fact-book 2000-2005

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2005-07-01

    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.)

  7. Future Bearing Surfaces in Total Hip Arthroplasty

    OpenAIRE

    Chang, Jun-Dong

    2014-01-01

    One of the most important issues in the modern total hip arthroplasty (THA) is the bearing surface. Extensive research on bearing surfaces is being conducted to seek an ideal bearing surface for THA. The ideal bearing surface for THA should have superior wear characteristics and should be durable, bio-inert, cost-effective, and easy to implant. However, bearing surfaces that are currently being implemented do not completely fulfill these requirements, especially for young individuals for whom...

  8. 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

  9. NASA total quality management 1989 accomplishments report

    Science.gov (United States)

    1990-01-01

    Described here are the accomplishments of NASA as a result of the use of Total Quality Management (TQM). The principles in practice which led to these process refinements are important cultural elements to any organization's productivity and quality efforts. The categories of TQM discussed here are top management leadership and support, strategic planning, focus on the customer, employee training and recognition, employee empowerment and teamwork, measurement and analysis, and quality assurance.

  10. Femoral Bone Plug in Total Knee Replacement.

    Science.gov (United States)

    Vulcano, Ettore; Regazzola, Gianmarco M V; Murena, Luigi; Ronga, Mario; Cherubino, Paolo; Surace, Michele F

    2015-10-01

    The intramedullary alignment guides used in total knee replacement disrupt the intramedullary vessels, resulting in greater postoperative blood loss. The use of an autologous bone plug to seal the intramedullary femoral canal has been shown to be effective in reducing postoperative bleeding. The authors present a simple technique to create a bone plug from the anterior chamfer femoral cut to perfectly seal the intramedullary canal of the femur. PMID:26488774

  11. Total workday control using Microsoft Outlook

    CERN Document Server

    Linenberger, Michael

    2008-01-01

    Total Workday Control Using Microsoft Outlook is a book for the over-extended office worker whose workday feels out of control. It shows how to regain command of an over-committed workday and an overflowing, unmanaged e-mail in box. It does this by teaching the author's system of time, task, and e-mail management, and it shows how to implement the system in Microsoft Outlook.

  12. 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...

  13. 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.)

  14. 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...

  15. Sign variation, the Grassmannian, and total positivity

    CERN Document Server

    Karp, Steven N

    2016-01-01

    The totally nonnegative Grassmannian is the set of k-dimensional subspaces V of R^n whose nonzero Pluecker coordinates all have the same sign. Gantmakher and Krein (1950) and Schoenberg and Whitney (1951) independently showed that V is totally nonnegative iff every vector in V, when viewed as a sequence of n numbers and ignoring any zeros, changes sign at most k-1 times. We generalize this result from the totally nonnegative Grassmannian to the entire Grassmannian, showing that if V is generic (i.e. has no zero Pluecker coordinates), then the vectors in V change sign at most m times iff certain sequences of Pluecker coordinates of V change sign at most m-k+1 times. We also give an algorithm which, given a non-generic V whose vectors change sign at most m times, perturbs V into a generic subspace whose vectors also change sign at most m times. We deduce that among all V whose vectors change sign at most m times, the generic subspaces are dense. These results generalize to oriented matroids. As an application o...

  16. Total synthesis of the indolizidine alkaloid tashiromine

    Directory of Open Access Journals (Sweden)

    McElhinney Alison D

    2008-01-01

    Full Text Available Abstract Background Tashiromine 1 is a naturally occurring indolizidine alkaloid. It has been the subject of thirteen successful total syntheses to date. Our own approach centres on the stereoselective construction of the indolizidine core by capture of an electrophilic acyliminium species by a pendant allylsilane. The key cyclisation precursor is constructed using olefin cross-metathesis chemistry, which has the potential to facilitate both racemic and asymmetric approaches, depending upon the choice of the allylsilane metathesis partner. Results The use of the allyltrimethylsilane cross-metathesis approach enables the rapid construction of the key cyclisation precursor 3 (3 steps from commercial materials, which undergoes acid-induced cyclisation to give the desired bicyclic indolizidine skeleton as a 96:4 mixture of diastereomers. Simple functional group interconversions allowed the completion of the total synthesis of racemic tashiromine in six steps (19% overall yield. Three chiral α-alkoxyallylsilanes (12,14 and 15 were prepared in enantioenriched form and their cross-metathesis reactions studied as part of a putative asymmetric approach to tashiromine. In the event, α-hydroxysilane 12 underwent isomerisation under the reaction conditions to acylsilane 17, while silanes 14 and 15 were unreactive towards metathesis. Conclusion A concise, stereoselective total synthesis of racemic tashiromine has been developed. Attempts to translate this into an asymmetric synthesis have thus far been unsuccessful.

  17. Total generating costs: coal and nuclear plants

    International Nuclear Information System (INIS)

    The study was confined to single and multi-unit coal- and nuclear-fueled electric-generating stations. The stations are composed of 1200-MWe PWRs; 1200-MWe BWRs; 800-and 1200-MWe High-Sulfur Coal units, and 800- and 1200-MWe Low-Sulfur Coal units. The total generating cost estimates were developed for commercial operation dates of 1985 and 1990; for 5 and 8% escalation rates, for 10 and 12% discount rates; and, for capacity factors of 50, 60, 70, and 80%. The report describes the methodology for obtaining annualized capital costs, levelized coal and nuclear fuel costs, levelized operation and maintenance costs, and the resulting total generating costs for each type of station. The costs are applicable to a hypothetical Middletwon site in the Northeastern United States. Plant descriptions with general design parameters are included. The report also reprints for convenience, summaries of capital cost by account type developed in the previous commercial electric-power cost studies. Appropriate references are given for additional detailed information. Sufficient detail is given to allow the reader to develop total generating costs for other cases or conditions

  18. Salivary total protein and experimental Coriolis sickness.

    Science.gov (United States)

    Igarashi, M; Reschke, M F; Henley, C; MacDonald, S; Kohl, R; Mizukoshi, K

    1993-01-01

    Symptomatic reporting has been used in quantifying the severity of motion sickness including Coriolis sickness. This study was designed to objectively examine if the dynamic changes of salivary protein concentration relate to the severity of Coriolis sickness. Healthy adults with normal vestibular function underwent a modified Coriolis Sickness Susceptibility Index (CSSI) test, utilizing a staircase profile. Salivary samples were obtained prior to stimulation, 15, 30, and 45 min following stimulus onset, and/or upon reaching "nausea-II" endpoint. Total protein concentration tended to rise over the initial 30 min of stimulation, and then level off or decline. A statistically significant difference was found between the pre-stimulation and 30 min samples. Although some variability existed among the subjects, the general pattern of changes along the time course was similar. An inverse correlation approaching statistical significance was found between control (non-stimulus) total protein levels, and minutes of Coriolis stimulation required to reach the "nausea-II" endpoint. Thus, baseline salivary total protein levels can be of use in predicting susceptibility of Coriolis sickness and other forms of motion sickness.

  19. Total quantum coherence and its applications

    Science.gov (United States)

    Yu, Chang-shui; Yang, Si-ren; Guo, Bao-qing

    2016-06-01

    Quantum coherence is the most fundamental feature of quantum mechanics. The usual understanding of it depends on the choice of the basis, that is, the coherence of the same quantum state is different within different reference framework. To reveal all the potential coherence, we present the total quantum coherence measures in terms of two different methods. One is optimizing maximal basis-dependent coherence with all potential bases considered and the other is quantifying the distance between the state and the incoherent state set. Interestingly, the coherence measures based on relative entropy and l_2 norm have the same form in the two different methods. In particular, we show that the measures based on the non-contractive l_2 norm are also a good measure different from the basis-dependent coherence. In addition, we show that all the measures are analytically calculable and have all the good properties. The experimental schemes for the detection of these coherence measures are also proposed by multiple copies of quantum states instead of reconstructing the full density matrix. By studying one type of quantum probing schemes, we find that both the normalized trace in the scheme of deterministic quantum computation with one qubit and the overlap of two states in quantum overlap measurement schemes can be well described by the change of total coherence of the probing qubit. Hence the nontrivial probing always leads to the change of the total coherence.

  20. Total Arterial Revascularisation in Left Ventricular Dysfunction

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The feasibility and safety of total arterial coronary revascularization with 2 arterial conduits in patients with impaired left ventricular function was evaluated. Data were prospectively collected on all patients with multiple vessel disease and moderately or severely impaired left ventricular function, who underwent coronary surgery with the intention of total arterial revascularization with 2 conduits between March 1995 and August 2002. One hundred and seventy-nine patients were included in the study. Acute coronary insufficiency was present in 3 patients and 43 had unstable angina. Severe left ventricular impairment was present in 29 patients. There were 17 redo operations including 3 redo-redo procedures. Eighty-two percent of patients had a Y graft configuration from the left internal mammary artery (right internal mammary artery 40. 8 %, radial artery 33.5 %,other 7.8 % ). The perioperative mortality was 2.2 %, myocardial infarction 1.7 % and stroke 0. 6 %.Total arterial revascularization in patients with ischaemic left ventricular dysfunction can be safely performed with 2 arterial conduits. The radial artery provides conduit length greater than the right internal mammary artery and allows full revascularization despite left ventricular dilatation.

  1. Total Emissions from Flaring in Kuwait Oilfields

    Directory of Open Access Journals (Sweden)

    K. K. AL-Hamad

    2008-01-01

    Full Text Available Kuwait is a major oil producing country and its economy directly depends on its export of crude and refined products. Kuwait Oil Company (KOC is responsible for all exploration and production of crude oil in Kuwait. These activities result in the emission of gaseous pollutants to the atmosphere, particularly from the flaring of undesirable product and excess gases. For environmental and resource conservation reasons, KOC is required to minimize the amount of gas flared in order to control and reduce the emissions of major pollutants in the State of Kuwait and neighbors countries. In the present study the total emissions of primary pollutants associated from flaring activities from Kuwait oil field have been estimated. An inventory records the annual emissions of air pollutants: NOX, SO2, CO, CO2, Methane and non-methane, Volatile Organic Compounds (VOC: resulting from oil production operations in the Kuwait Oil Fields. The emissions are generated from various point sources and aggregated to have total pollutants load of ambient air. Emissions of flaring pollutants are associated with all operations in Oil fields, Gathering Centers (GC, Boaster Stations (BS, Tank areas and other oil production related activities. The objective of this work was to obtain an accurate estimation of the total flare emission from oil production activities thereby aiding the effective planning of mitigation strategies to control and reduce the pollution from crude related operation.

  2. Total quantum coherence and its applications

    Science.gov (United States)

    Yu, Chang-shui; Yang, Si-ren; Guo, Bao-qing

    2016-09-01

    Quantum coherence is the most fundamental feature of quantum mechanics. The usual understanding of it depends on the choice of the basis, that is, the coherence of the same quantum state is different within different reference framework. To reveal all the potential coherence, we present the total quantum coherence measures in terms of two different methods. One is optimizing maximal basis-dependent coherence with all potential bases considered and the other is quantifying the distance between the state and the incoherent state set. Interestingly, the coherence measures based on relative entropy and l_2 norm have the same form in the two different methods. In particular, we show that the measures based on the non-contractive l_2 norm are also a good measure different from the basis-dependent coherence. In addition, we show that all the measures are analytically calculable and have all the good properties. The experimental schemes for the detection of these coherence measures are also proposed by multiple copies of quantum states instead of reconstructing the full density matrix. By studying one type of quantum probing schemes, we find that both the normalized trace in the scheme of deterministic quantum computation with one qubit and the overlap of two states in quantum overlap measurement schemes can be well described by the change of total coherence of the probing qubit. Hence the nontrivial probing always leads to the change of the total coherence.

  3. Total body irradiation: current indications; L`irradiation corporelle totale: les indications actuelles

    Energy Technology Data Exchange (ETDEWEB)

    Giraud, P.; Danhier, S.; Dubray, B.; Cosset, J.M. [Institut Curie, 75 - Paris (France)

    1998-05-01

    The choice of dose and fractionation for total body irradiation is made difficult by the large number of considerations to be taken into account. The outcome of bone marrow transplantation after total body irradiation can be understood in terms of tumor cell killing, engraftment, and normal tissue damage, each of these endpoints being influenced by irradiation-, disease-, transplant-, and patient- related factors. Interpretation of clinical data is further hampered by the overwhelming influence of logistic constraints, the small numbers of randomized studies, and the concomitant variations in total dose and fraction size or dose rate. So far, three cautious conclusions can be drawn in order to tentatively adapt the total body irradiation schedule to clinically-relevant situations. Firstly, the organs at risk for normal tissue damage (lung, liver, lens, kidney) are protected by delivering small doses per fraction at low dose rate. This suggests that, when toxicity is at stake (e.g. in children), fractionated irradiation should be preferred, provided that inter-fraction intervals are long enough. Secondly, fractionated irradiation should be avoided in case of T-cell depleted transplant, given the high risk of graft rejection in this setting. An alternative would be to increase total (or fractional) dose of fractionated total body irradiation, but this approach is likely to induce more normal tissue toxicity. Thirdly, clinical data have shown higher relapse rates in chronic myeloid leukemia after fractionated or low dose rate total body irradiation, suggesting that fractionated irradiation should not be recommended, unless total (or fractional) dose is increased. Total body irradiation-containing regimens, primarily cyclophosphamide / total body irradiation, are either equivalent to or better than the chemotherapy-only regimens, primarily busulfan / cyclophosphamide. Busulfan / cyclophosphamide certainly represents a reasonable alternative, especially in patients who

  4. Introduction of total knee arthroplasty in Lithuania

    Science.gov (United States)

    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. As in the hip replacement study, only patients with osteoarthritis (OA) were included. Primary knee arthroplasties without patellar resurfacing were included, and the endpoint was revision for any reason other than addition of a patellar component. Results We found that the cumulative revision rate was not statistically significantly different between the groups. The revision pattern was different, however, and we observed 24 isolated patellar component additions in Sweden, but none in Klaipeda. Interpretation Contrary to the results of our previous hip arthroplasty study, the cumulative revision rate after total knee arthroplasty was similar in the two groups. This suggests that compared to hip arthroplasty, the outcome of total knee arthroplasty was less dependent on surgical experience. The large difference regarding isolated patellar component additions may be explained by long-term accumulation of severe OA cases in Lithuania. To patients subject to a newly introduced surgical treatment offering great improvement in quality of life, patellofemoral pain may be a minor problem. Furthermore, patellar problems may not have seemed particularly relevant for the surgeons, considering the disability of other patients waiting to be treated. PMID:19297790

  5. Assessment of total efficiency in adiabatic engines

    Science.gov (United States)

    Mitianiec, W.

    2016-09-01

    The paper presents influence of ceramic coating in all surfaces of the combustion chamber of SI four-stroke engine on working parameters mainly on heat balance and total efficiency. Three cases of engine were considered: standard without ceramic coating, fully adiabatic combustion chamber and engine with different thickness of ceramic coating. Consideration of adiabatic or semi-adiabatic engine was connected with mathematical modelling of heat transfer from the cylinder gas to the cooling medium. This model takes into account changeable convection coefficient based on the experimental formulas of Woschni, heat conductivity of multi-layer walls and also small effect of radiation in SI engines. The simulation model was elaborated with full heat transfer to the cooling medium and unsteady gas flow in the engine intake and exhaust systems. The computer program taking into account 0D model of engine processes in the cylinder and 1D model of gas flow was elaborated for determination of many basic engine thermodynamic parameters for Suzuki DR-Z400S 400 cc SI engine. The paper presents calculation results of influence of the ceramic coating thickness on indicated pressure, specific fuel consumption, cooling and exhaust heat losses. Next it were presented comparisons of effective power, heat losses in the cooling and exhaust systems, total efficiency in function of engine rotational speed and also comparison of temperature inside the cylinder for standard, semi-adiabatic and full adiabatic engine. On the basis of the achieved results it was found higher total efficiency of adiabatic engines at 2500 rpm from 27% for standard engine to 37% for full adiabatic engine.

  6. Total Hip Arthroplasty in Mucopolysaccharidosis Type IH

    Directory of Open Access Journals (Sweden)

    S. O'hEireamhoin

    2011-01-01

    Full Text Available Children affected by mucopolysaccharidosis (MPS type IH (Hurler Syndrome, an autosomal recessive metabolic disorder, are known to experience a range of musculoskeletal manifestations including spinal abnormalities, hand abnormalities, generalised joint stiffness, genu valgum, and hip dysplasia and avascular necrosis. Enzyme therapy, in the form of bone marrow transplantation, significantly increases life expectancy but does not prevent the development of the associated musculoskeletal disorders. We present the case of a 23-year-old woman with a diagnosis of Hurler syndrome with a satisfactory result following uncemented total hip arthroplasty.

  7. Total-variation regularization with bound constraints

    Energy Technology Data Exchange (ETDEWEB)

    Chartrand, Rick [Los Alamos National Laboratory; Wohlberg, Brendt [Los Alamos National Laboratory

    2009-01-01

    We present a new algorithm for bound-constrained total-variation (TV) regularization that in comparison with its predecessors is simple, fast, and flexible. We use a splitting approach to decouple TV minimization from enforcing the constraints. Consequently, existing TV solvers can be employed with minimal alteration. This also makes the approach straightforward to generalize to any situation where TV can be applied. We consider deblurring of images with Gaussian or salt-and-pepper noise, as well as Abel inversion of radiographs with Poisson noise. We incorporate previous iterative reweighting algorithms to solve the TV portion.

  8. Tikhonov Regularization and Total Least Squares

    DEFF Research Database (Denmark)

    Golub, G. H.; Hansen, Per Christian; O'Leary, D. P.

    2000-01-01

    Discretizations of inverse problems lead to systems of linear equations with a highly ill-conditioned coefficient matrix, and in order to compute stable solutions to these systems it is necessary to apply regularization methods. We show how Tikhonov's regularization method, which in its original...... formulation involves a least squares problem, can be recast in a total least squares formulation suited for problems in which both the coefficient matrix and the right-hand side are known only approximately. We analyze the regularizing properties of this method and demonstrate by a numerical example that......, in certain cases with large perturbations, the new method is superior to standard regularization methods....

  9. Total Pelvic Exenteration for Gynecologic Malignancies

    Directory of Open Access Journals (Sweden)

    Elisabeth J. Diver

    2012-01-01

    Full Text Available Total pelvic exenteration (PE is a radical operation, involving en bloc resection of pelvic organs, including reproductive structures, bladder, and rectosigmoid. In gynecologic oncology, it is most commonly indicated for the treatment of advanced primary or locally recurrent cancer. Careful patient selection and counseling are of paramount importance when considering someone for PE. Part of the evaluation process includes comprehensive assessment to exclude unresectable or metastatic disease. PE can be curative for carefully selected patients with gynecologic cancers. Major complications can be seen in as many as 50% of patients undergoing PE, underscoring the need to carefully discuss risks and benefits of this procedure with patients considering exenterative surgery.

  10. TotalFinaElf Factbook 2002

    International Nuclear Information System (INIS)

    This report presents the activities and results of the Group Total-Fina-Elf for the year 2002. 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.)

  11. Total synthesis and biological investigation of (-)-promysalin.

    Science.gov (United States)

    Steele, Andrew D; Knouse, Kyle W; Keohane, Colleen E; Wuest, William M

    2015-06-17

    Compounds that specifically target pathogenic bacteria are greatly needed, and identifying the method by which they act would provide new avenues of treatment. Herein we report the concise, high-yielding total synthesis (eight steps, 35% yield) of promysalin, a natural product that displays antivirulence phenotypes against pathogenic bacteria. Guided by bioinformatics, four diastereomers were synthesized, and the relative and absolute stereochemistries were confirmed by spectral and biological analysis. Finally, we show for the first time that promysalin displays two antivirulence phenotypes: the dispersion of mature biofilms and the inhibition of pyoverdine production, hinting at a unique pathogenic-specific mechanism of action.

  12. A journey into TQM (total quality management).

    Science.gov (United States)

    Jackson, M B

    1994-01-01

    Total quality management (TQM) which has been implemented for some time in industry and more recently in hospitals is just beginning to come to long term care organizations. Directors of Nursing can prepare themselves for such a program in their facility by learning from the experience of long term care facilities that have implemented TQM. This is part one of a two part series which describes the implementation process used and a discussion of problems encountered. The second article which will appear in a later issue describes the experience and findings of one project team-the nursing documentation team.

  13. ARE THERE LIMITS TO TOTAL QUALITY MANAGEMENT ?

    Directory of Open Access Journals (Sweden)

    Firdaus Firdaus

    2000-01-01

    Full Text Available Although TQM could solve every problems but it does not mean that TQM is unlimited. There are several limitations on TQM application, some examples from international cases is taken to show the failure of TQM implementation. The understanding of TQM philosophy is really necessary. Abstract in Bahasa Indonesia : Meskipun TQM dapat menyelesaikan semua masalah tetapi bukan berarti bahwa TQM tanpa batas. Ada beberapa keterbatasan penerapan TQM yang berujung pada beberapa kasus dunia yang dapat diambil sebagai contoh dari kegagalan penerapan TQM secara baik dan benar. Untuk itu diperlukan pemahaman filosophi TQM secara tepat. Kata kunci: total quality management, keterbatasan TQM

  14. Security Systems Consideration: A Total Security Approach

    Science.gov (United States)

    Margariti, S. V.; Meletiou, G.; Stergiou, E.; Vasiliadis, D. C.; Rizos, G. E.

    2007-12-01

    The "safety" problem for protection systems is to determine in a given situation whether a subject can acquire a particular right to an object. Security and audit operation face the process of securing the application on computing and network environment; however, storage security has been somewhat overlooked due to other security solutions. This paper identifies issues for data security, threats and attacks, summarizes security concepts and relationships, and also describes storage security strategies. It concludes with recommended storage security plan for a total security solution.

  15. Total Variation and Tomographic Imaging from Projections

    DEFF Research Database (Denmark)

    Hansen, Per Christian; Jørgensen, Jakob Heide

    2011-01-01

    Total Variation (TV) regularization is a powerful technique for image reconstruction tasks such as denoising, in-painting, and deblurring, because of its ability to produce sharp edges in the images. In this talk we discuss the use of TV regularization for tomographic imaging, where we compute a 2D...... or 3D reconstruction from noisy projections. We demonstrate that for a small signal-to-noise ratio, this new approach allows us to compute better (i.e., more reliable) reconstructions than those obtained by classical methods. This is possible due to the use of the TV reconstruction model, which...

  16. Total Routhian surface calculation for 127I

    International Nuclear Information System (INIS)

    The Total Routhian Surface (TRS) calculation is a very useful and well known way to understand the rotational motion of the atomic nuclei theoretically. The evolution of the deformations during the process of nuclear rotation can be studied theoretically under the framework of TRS. The quadrupole and triaxial deformation play crucial roles in the rotational properties of nuclei. The TRS formalism was developed mainly based on the macroscopic-microscopic model. The aim of the present work is to study the positive parity yrast rotational structure of 127I in terms of deformation, under the framework of macroscopic-microscopic model

  17. Total on-line purchasing system (TOPS)

    Energy Technology Data Exchange (ETDEWEB)

    Collins, N.

    1995-11-01

    The Information Management Division (IMD) at LLNL is developing a new purchasing system for the Procurement Department. The first major development of this new system is called, {open_quotes}Total On-Line Purchasing System{close_quotes} (TOPS). TOPS will help speed up the requisitioning process by having requisitions electronically entered by requesters and electronically sent to buyers to be put on Purchase Orders. The new purchasing system will use Electronic Commerce (EC)/Electronic Data Interchange (EDI), to help increase transaction flows for shipping notices, RFQs, Quotes, Purchase Orders, and Invoices. ANSI X.12 is the EDI standard that this new EC will use.

  18. PENDEKATAN TOTAL QUALITY MANAGEMENT PRODUK BROILER TOLAKAN

    Directory of Open Access Journals (Sweden)

    Zeetpy Maisana

    2012-11-01

    Full Text Available ABSTRACTThe purpose of this study was to analyze rejected product in slaughterhouse division using total quality management approach. The secondary data were collected from the company archives and judgmental sampling was used to collect primary data from six experienced respondents. The analysis method used was total quality management, include stratification, Pareto diagrams, control charts, fishbone diagrams, and quality function deployment. The findings of this study showed that the use of line production system by the slaughterhouse to produce the product; where products’ redness/bruises, size uniformity, bloodless feature, incorrect delivery, delivery delay, and damaged package were the cause of product rejection. The strategies ordered based on the priority to improve the management quality are: tools repair and replacement, creating quality based projects, build an information system between the production lines, training and seminar. The managerial implications of the study suggested the slaughterhouse to replace or repair the plucker, scalder and automatic weighing machine. It also suggested the slaughterhouse to tighten the span of control in the chilling room to maintain product freshness.Keywords: rejected product analysis, TQM, QFD, chicken slaughterhouse, carcassABSTRAKPenelitian ini bertujuan menganalisis produk tolakan pada rumah potong ayam melalui pendekatan total quality management. Pengumpulan data sekunder penelitian diperoleh dari arsip perusahaan dan judgemental sampling digunakan terhadap enam responden ahli untuk memperoleh data primer penelitian. Metode analisis data yang digunakan total quality management, meliputi stratifikasi, diagram pareto, peta kendali, diagram tulang ikan, dan quality function deployment.  Hasil penelitian menunjukkan penggunaan sistem lini produksi pada proses produksi di perusahaan, dimana memar pada produk, keseragaman ukuran, kesegaran produk, pengiriman tidak sesuai pesanan

  19. Total internal reflection tomography of small objects

    International Nuclear Information System (INIS)

    The multiple signal classification (MUSIC) imaging method is applied to determine the locations of a collection of small anisotropic spherical scatterers in the framework of the total internal reflection tomography. Multiple scattering between scatterers is considered and the inverse scattering problem is nonlinear, which, however, is solved by the proposed fast analytical approach where no associated forward problem is iteratively evaluated. The paper also discusses the role of the polarization of incidence waves, the incidence angle, the separation of scatterers from the surface of the substrate, and the level of noise on the resolution of imaging.

  20. Vaginal mass following uncemented total hip arthroplasty

    Directory of Open Access Journals (Sweden)

    Young-Soo Shin

    2014-01-01

    Full Text Available A 53-year-old woman developed a vaginal mass following an uncemented total hip arthroplasty. The mass was in direct communication with the hip through an acetabular medial wall defect after loosening of the acetabular component. The mass formation was caused simultaneously by changes secondary to polyethylene wear, a tiny delamination of the porous titanium mesh coating and a broken antirotational tab on the acetabular cup, all of which may have served as sources of metal particles. A careful evaluation of the patient′s history, symptoms, X-ray findings and computed tomography scans should always be performed to ensure accurate diagnosis.

  1. Total Syntheses of Periconiasins A-E.

    Science.gov (United States)

    Tian, Chong; Lei, Xiaoqiang; Wang, Yuanhao; Dong, Zhen; Liu, Gang; Tang, Yefeng

    2016-06-01

    The first and collective total syntheses of periconiasins A-E, a group of naturally occurring cytochalasans, were achieved by a series of rationally designed or bioinspired transformations. Salient features of the syntheses include a tandem aldol condensation/Grob fragmentation to assemble the linear polyketide-amino acid hybrid precursor, a Diels-Alder macrocylization to construct the 9/6/5 tricyclic core of periconiasins A-C, and a transannular carbonyl-ene reaction to forge the polycyclic framework of periconiasins D and E. PMID:27121397

  2. Heterotopic ossification following lumbar total disc replacement

    OpenAIRE

    Park, Se-Jun; Kang, Kyung-Jung; Shin, Seong-Kee; Chung, Sung-Soo; Lee, Chong-Suh

    2010-01-01

    The main goal of total disc replacement (TDR) is to preserve motion. Despite reports of good clinical outcomes, various degrees of heterotopic ossification after TDR have been reported. The purpose of this study was to investigate the prevalence and its clinical relevance of heterotopic ossification. We evaluated 65 consecutive patients (82 segments) with mean follow-up duration of 45 months (range, 12–88 months). Two kinds of prosthesis, ProDisc® for 75 segments (91.5%) and CHARITETM for sev...

  3. Total down to work for Chtokman's gas

    International Nuclear Information System (INIS)

    In the framework of the exploitation contract signed with Gazprom, Total group, partner of the project with StatoilHydro, has started the feasibility study for the huge Chtokman gas field in Russia (Barents sea). A definitive investment decision should be given within less a year. The pre-project phase started in summer 2008 but nothing has been decided yet. Russia has two big projects in competition: Chtokman and Kharasavey in Yamal province. Considering the extreme climate conditions and the technical challenges, Russia will need the experience of foreign partners. (J.S.)

  4. Total knee arthroplasty in vascular malformation

    Directory of Open Access Journals (Sweden)

    Harish Bhende

    2015-01-01

    Full Text Available In Klippel–Trenaunay syndrome, vascular malformations are not only in skin and superficial soft tissues but also in deep tissues like muscles bones and joints. It is well documemted that these recurrent intraarticular bleeds can cause early arthritis and joint pain. Performing arthroplasty in such patients is difficult and fraught with complications. We describe such a case where navigated total knee arthroplasty was performed with success to avoid the problems of intra medullary alignment used in the presence of intra medullary vascular malformations. We also suggest certain measures when knee arthroplasty is considered in such patients.

  5. Total synthesis of insect antifeedant drimane sesquiterpenes.

    OpenAIRE

    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 oxidized at C-11 and/or C-12 and often at other sites as well (see figure 8.1).A few rearranged drimanes, e.g., (+)-colorata-4(13),8-dienolide 6 , and (-)-muzigadial 7 , are also isolated from natural products. The re...

  6. Total ankle arthroplasty: An imaging overview

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Da Rae; Choi, Yun Sun; Chun, Ka Young; Jung, Yoon Young; Kim, Jin Su; Young, Ki Won [Eulji Hospital, Eulji University, Seoul (Korea, Republic of); Potter, Hollis G.; Li, Angela E. [Dept. of Radiology and Imaging, Hospital for Special Surgery, New York (United States)

    2016-06-15

    With advances in implant technology, total ankle arthroplasty (TAA) has become an increasingly popular alternative to arthrodesis for the management of end-stage ankle arthritis. However, reports in the literature do not focus on the imaging features of TAA. Through a literature review, we demonstrate basic design features of the current ankle arthroplasty system, and the normal and abnormal postoperative imaging features associated with such devices. Pre- and postoperative evaluations of ankle arthroplasty mainly include radiography; in addition, computed tomography and magnetic resonance imaging provide further characterization of imaging abnormalities. Familiarization with multimodal imaging features of frequent procedural complications at various postoperative intervals is important in radiological practice.

  7. Total skin electron irradiation in mycosis fungoides

    Energy Technology Data Exchange (ETDEWEB)

    van Vloten, W.A.; Vermeij, J.; de Vroome, H.

    1977-01-01

    Total skin irradiation with fast electrons (4 MeV, 3500 rad) was applied in 10 cases of histologically proven mycosis fungoides without any signs of internal dissemination. The technique is described. Complete disappearance of both lesions and symptoms occurred in all patients after treatment. However, half of the patients relapsed after the initial irradiation and were subsequently treated with a booster dose of 1000 rad 4 MeV electrons or with topical nitrogen mustard. Irradiation with fast electrons seems to be of great importance in the treatment of mycosis fungoides.

  8. Scientific observations at total solar eclipses

    OpenAIRE

    Pasachoff, Jay M.

    2009-01-01

    The occasion of the longest totality of an eclipse in the 18 yr 11⅓ 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...

  9. Segmental blood pressure after total hip replacement

    DEFF Research Database (Denmark)

    Gebuhr, Peter Henrik; Soelberg, M; Henriksen, Jens Henrik Sahl

    1992-01-01

    Twenty-nine patients due to have a total hip replacement had their systemic systolic and segmental blood pressures measured prior to operation and 1 and 6 weeks postoperatively. No patients had signs of ischemia. The segmental blood pressure was measured at the ankle and at the toes. A significant...... drop was found in all pressures 1 week postoperatively. The decrease followed the systemic pressure and was restored to normal after 6 weeks. In a group of six patients with preoperatively decreased ankle pressure, a significant transient further decrease in the ankle-toe gradient pressure was found...

  10. Total Ankle Arthroplasty: An Imaging Overview.

    Science.gov (United States)

    Kim, Da-Rae; Choi, Yun Sun; Potter, Hollis G; Li, Angela E; Chun, Ka-Young; Jung, Yoon Young; Kim, Jin-Su; Young, Ki-Won

    2016-01-01

    With advances in implant technology, total ankle arthroplasty (TAA) has become an increasingly popular alternative to arthrodesis for the management of end-stage ankle arthritis. However, reports in the literature do not focus on the imaging features of TAA. Through a literature review, we demonstrate basic design features of the current ankle arthroplasty system, and the normal and abnormal postoperative imaging features associated with such devices. Pre- and postoperative evaluations of ankle arthroplasty mainly include radiography; in addition, computed tomography and magnetic resonance imaging provide further characterization of imaging abnormalities. Familiarization with multimodal imaging features of frequent procedural complications at various postoperative intervals is important in radiological practice.

  11. [Bilateral vocal cord paresis after total thyroidectomy].

    Science.gov (United States)

    Dralle, H; Neu, J; Musholt, T J; Nies, C

    2016-01-01

    A 66-year-old female patient complained of hoarseness and dyspnea under exertion following total thyroidectomy. Due to a faulty operating technique both nerves to the vocal cords were damaged. From the operation report it emerged that the dissection was carried out by protecting the border lamellae but the recurrent laryngeal nerve could not be found on both sides. This article presents the external expert opinion, the decision of the arbitration board and the assessment of the case by two specialist physicians. PMID:26683653

  12. A Combination of Varying Column Pressure and Total Reflux—Total Efflux in Batch Distillation Operation

    Institute of Scientific and Technical Information of China (English)

    ZHANGWeijiang; QUHongmei; 等

    2002-01-01

    A novel operation of batch distillation-combination of varying colum pressure and total reflux-total efflux is studied experimentally. In the operation, the product is accumulated at the top of the column under total reflux and then drained off completely, and the column pressure is varying in the whole process. This process has been industrialized successfully with large profits. The conventional mode of batch distillation is improved by this method effectively: the separation eficiency and the yield of product are increased greatly, the operation time is shortened and the production cost is cut down. Moreover, the amount of condensation water is decreased and the over-high reboiler temperature is lowered.

  13. Methods development for total organic carbon accountability

    Science.gov (United States)

    Benson, Brian L.; Kilgore, Melvin V., Jr.

    1991-01-01

    This report describes the efforts completed during the contract period beginning November 1, 1990 and ending April 30, 1991. Samples of product hygiene and potable water from WRT 3A were supplied by NASA/MSFC prior to contract award on July 24, 1990. Humidity condensate samples were supplied on August 3, 1990. During the course of this contract chemical analyses were performed on these samples to qualitatively determine specific components comprising, the measured organic carbon concentration. In addition, these samples and known standard solutions were used to identify and develop methodology useful to future comprehensive characterization of similar samples. Standard analyses including pH, conductivity, and total organic carbon (TOC) were conducted. Colorimetric and enzyme linked assays for total protein, bile acid, B-hydroxybutyric acid, methylene blue active substances (MBAS), urea nitrogen, ammonia, and glucose were also performed. Gas chromatographic procedures for non-volatile fatty acids and EPA priority pollutants were also performed. Liquid chromatography was used to screen for non-volatile, water soluble compounds not amenable to GC techniques. Methods development efforts were initiated to separate and quantitate certain chemical classes not classically analyzed in water and wastewater samples. These included carbohydrates, organic acids, and amino acids. Finally, efforts were initiated to identify useful concentration techniques to enhance detection limits and recovery of non-volatile, water soluble compounds.

  14. Total quality drives nuclear plant improvements

    International Nuclear Information System (INIS)

    Total quality (TQ) at Carolina Power and Light (CP and L) is fulfilling a 1985 vision of Sherwood H. Smith, Jr., CP and L's chairman, president, and chief executive officer. The TQ concept has provided a way for employees to align their creative energies toward meeting the business needs of the company. Throughout CP and L, TQ has been recognized as the vehicle for reducing operating costs and improving customer satisfaction. Within the nuclear organization, application of the TQ process has helped to improve communications, resolve challenges, and provide more consistent work practices among CP and L's three nuclear plants. Total quality was introduced from the top down, with initial benefits coming from team interactions. Senior management at CP and L defined the corporate expectations and outlined the training requirements for implementing TQ. Management staffs at each organizational level became steering committees for TQ team activities within their departments. Teams of employees most knowledgeable about a given work area were empowered to solve problems or overcome obstacles related to that work area. Employees learned to become better team players and to appreciate the quality of decisions reached through group consensus. Now, formalized methods that started TQ are becoming part of the day-to-day work ethic

  15. Deformation analysis with Total Least Squares

    Directory of Open Access Journals (Sweden)

    M. Acar

    2006-01-01

    Full Text Available Deformation analysis is one of the main research fields in geodesy. Deformation analysis process comprises measurement and analysis phases. Measurements can be collected using several techniques. The output of the evaluation of the measurements is mainly point positions. In the deformation analysis phase, the coordinate changes in the point positions are investigated. Several models or approaches can be employed for the analysis. One approach is based on a Helmert or similarity coordinate transformation where the displacements and the respective covariance matrix are transformed into a unique datum. Traditionally a Least Squares (LS technique is used for the transformation procedure. Another approach that could be introduced as an alternative methodology is the Total Least Squares (TLS that is considerably a new approach in geodetic applications. In this study, in order to determine point displacements, 3-D coordinate transformations based on the Helmert transformation model were carried out individually by the Least Squares (LS and the Total Least Squares (TLS, respectively. The data used in this study was collected by GPS technique in a landslide area located nearby Istanbul. The results obtained from these two approaches have been compared.

  16. Cortical bone total ossicular replacement prosthesis

    Directory of Open Access Journals (Sweden)

    Manu Malhotra

    2014-01-01

    Full Text Available Objectives: Evaluate an autologous cortical bone total ossicular replacement prosthesis (B TORP made of cortical bone for cost effective and sustainable hearing results. Materials and Methods: A prospective study was undertaken in the patients who underwent tympanoplasty with new B-TORP from January 2011 to December 2011. All patients had an absent superstructure of the stapes and long process of the incus due to chronic otitis media. Totally 40 patients were evaluated. Hearing results were evaluated using four-frequency average pure tone air conduction and air-bone gap (ABG measured at 0.5, 1, 2, and 3 kHz after a period of 12 months. Pre- and post-operative continuous variables were compared using a paired t-test and data from unequal groups were assessed for significant differences using unpaired t-test. Results: Successful rehabilitation of the ABG to 20 dB or less was achieved in 95% of patients. Overall mean improvement in ABG was 25.8 ± 5.6 dB, which was statistically significant (t = 26.8, P 0.5. Conclusion: The new autologous B-TORP provides sustainable hearing improvement and is bio-compatible, stable, and magnetic resonance imaging compatible.

  17. Total Site Heat Integration Considering Pressure Drops

    Directory of Open Access Journals (Sweden)

    Kew Hong Chew

    2015-02-01

    Full Text Available Pressure drop is an important consideration in Total Site Heat Integration (TSHI. This is due to the typically large distances between the different plants and the flow across plant elevations and equipment, including heat exchangers. Failure to consider pressure drop during utility targeting and heat exchanger network (HEN synthesis may, at best, lead to optimistic energy targets, and at worst, an inoperable system if the pumps or compressors cannot overcome the actual pressure drop. Most studies have addressed the pressure drop factor in terms of pumping cost, forbidden matches or allowable pressure drop constraints in the optimisation of HEN. This study looks at the implication of pressure drop in the context of a Total Site. The graphical Pinch-based TSHI methodology is extended to consider the pressure drop factor during the minimum energy requirement (MER targeting stage. The improved methodology provides a more realistic estimation of the MER targets and valuable insights for the implementation of the TSHI design. In the case study, when pressure drop in the steam distribution networks is considered, the heating and cooling duties increase by 14.5% and 4.5%.

  18. Surgical approaches for total knee arthroplasty.

    Science.gov (United States)

    Vaishya, Raju; Vijay, Vipul; Demesugh, Daniel Mue; Agarwal, Amit Kumar

    2016-01-01

    There are various surgical approaches to the knee joint and its surrounding structures and such approaches are generally designed to allow the best access to an area of pathology whilst safeguarding important surrounding structures. Controversy currently surrounds the optimal surgical approach for total knee arthroplasty (TKA). The medial parapatellar arthrotomy, or anteromedial approach, has been the most used and has been regarded as the standard approach for exposure of the knee joint. It provides extensive exposure and is useful for open anterior cruciate ligament reconstruction, total knee replacement, and fixation of intra-articular fractures. Because this approach has been implicated in compromise of the patellar circulation, some authors have advocated the subvastus, midvastus, and trivector approaches for exposure of the knee joint. While these approaches expose the knee from the medial side, the anterolateral approach exposes the knee joint from the lateral side. With careful planning and arthrotomy selection, the anterior aspect of the joint can be adequately exposed for TKA in different clinical scenarios. PMID:27182142

  19. Total hemispherical emissivity of Inconel 718

    International Nuclear Information System (INIS)

    Highlights: • We have measured the total hemispherical emissivity for Inconel 718 from about 600–1250 K. • Oxidation in air at 1073 K resulted in an increase in emissivity. • Sandblasting of Inconel 718 was also observed to increase the emissivity. • Coating of graphite powder onto the ‘as-received’ Inconel 718 showed no increase in the emissivity. • Coating of graphite powder onto the 220 grit sandblasted Inconel 718 did show an increase in emissivity. - Abstract: Total hemispherical emissivity for Inconel 718 was measured in anticipation of its application in Very High Temperature Gas Reactors (VHTRs). A majority of current emissivity data for Inconel 718 is in the form of spectral measurements. The data presented here were obtained with an experimental apparatus based on the standard ASTM C835-06 for total hemispherical emittance. Measurements of Inconel 718 were made for four different surface types including: (i) ‘as-received’ from the manufacturer, (ii) oxidized in air and humidified helium, (iii) sandblasted with aluminum oxide powder, and (iv) with a thin coating of nuclear grade graphite powder (grade NGB-18). The emissivity for the ‘as-received’ sample ranged from 0.21 to 0.28 in the temperature interval from 760 K to 1275 K. Oxidation in air at 1073 K resulted in an increase in emissivity into the range from 0.2 at 650 K to 0.52 at 1200 K. There was no dependence on the oxidation times studied here. Oxidation with humidified helium at 1073 K produced less of an increase in emissivity than the oxidation in air but there was an increase up to the range from 0.2 at 600 K to 0.35 at 1200 K. Sandblasting of Inconel 718 was also observed to increase the emissivity up to the range from 0.43 at 780 K to 0.53 at 1270 K when 60 grit sized powder was used and up to the range from 0.45 at 683 K to 0.57 at 1267 K when 120 and 220 grit sized powders were used. Coating of graphite powder onto the ‘as-received’ Inconel 718 showed no increase

  20. Total hemispherical emissivity of Inconel 718

    Energy Technology Data Exchange (ETDEWEB)

    Keller, Benjamin P.; Nelson, Shawn E.; Walton, Kyle L.; Ghosh, Tushar K.; Tompson, Robert V.; Loyalka, Sudarshan K., E-mail: LoyalkaS@missouri.edu

    2015-06-15

    Highlights: • We have measured the total hemispherical emissivity for Inconel 718 from about 600–1250 K. • Oxidation in air at 1073 K resulted in an increase in emissivity. • Sandblasting of Inconel 718 was also observed to increase the emissivity. • Coating of graphite powder onto the ‘as-received’ Inconel 718 showed no increase in the emissivity. • Coating of graphite powder onto the 220 grit sandblasted Inconel 718 did show an increase in emissivity. - Abstract: Total hemispherical emissivity for Inconel 718 was measured in anticipation of its application in Very High Temperature Gas Reactors (VHTRs). A majority of current emissivity data for Inconel 718 is in the form of spectral measurements. The data presented here were obtained with an experimental apparatus based on the standard ASTM C835-06 for total hemispherical emittance. Measurements of Inconel 718 were made for four different surface types including: (i) ‘as-received’ from the manufacturer, (ii) oxidized in air and humidified helium, (iii) sandblasted with aluminum oxide powder, and (iv) with a thin coating of nuclear grade graphite powder (grade NGB-18). The emissivity for the ‘as-received’ sample ranged from 0.21 to 0.28 in the temperature interval from 760 K to 1275 K. Oxidation in air at 1073 K resulted in an increase in emissivity into the range from 0.2 at 650 K to 0.52 at 1200 K. There was no dependence on the oxidation times studied here. Oxidation with humidified helium at 1073 K produced less of an increase in emissivity than the oxidation in air but there was an increase up to the range from 0.2 at 600 K to 0.35 at 1200 K. Sandblasting of Inconel 718 was also observed to increase the emissivity up to the range from 0.43 at 780 K to 0.53 at 1270 K when 60 grit sized powder was used and up to the range from 0.45 at 683 K to 0.57 at 1267 K when 120 and 220 grit sized powders were used. Coating of graphite powder onto the ‘as-received’ Inconel 718 showed no increase

  1. Evaluation of salivary sialic acid, total protein, and total sugar in oral cancer: A preliminary report

    Directory of Open Access Journals (Sweden)

    Sanjay P

    2008-01-01

    Full Text Available Aim: Detection of cancer at the early stage is of utmost importance to decrease the morbidity and mortality of the disease. Apart from the conventional biopsy, noninvasive methods like analysis of saliva may provide a cost-effective approach for screening a large population. Thus, this study aimed to estimate salivary levels of sialic acid, total protein, and total sugar in the oral cancer patients and in healthy control group to evaluate their role in diagnosis and prognosis of oral cancer. Study Design: Unstimulated whole saliva samples were collected from 30 healthy controls (Group I and 30 squamous cell carcinoma patients (group II. Estimations of salivary levels of sialic acid, total protein, and total sugar were performed. This was correlated histopathologically with the grades of carcinoma. Statistical Analysis and Results: The Student′s ′ t ′ test and multivariate regression analysis were performed. The results showed that salivary levels of total protein, total sugar, protein-bound sialic acid, and free sialic acid were significantly higher in oral cancer patients compared to those of normal healthy controls ( P values in all the results were less than 0.001. The salivary free sialic acid levels were found to be significantly higher in well-differentiated squamous cell carcinoma than in moderately differentiated carcinoma ( P < 0.001. However, protein-bound sialic acid, total proteins, and total sugars did not show any statistical significance between well and moderately differentiated carcinomas. Conclusion: Biochemical analysis of saliva can be used in early detection of cancer and is best correlated with histopathological degree of squamous cell carcinoma.

  2. Positron interactions with water–total elastic, total inelastic, and elastic differential cross section measurements

    Energy Technology Data Exchange (ETDEWEB)

    Tattersall, Wade [Centre for Antimatter-Matter Studies, Research School of Physics and Engineering, The Australian National University, Canberra, ACT 0200 (Australia); Centre for Antimatter-Matter Studies, School of Engineering and Physical Sciences, James Cook University, Townsville, 4810 Queensland (Australia); Chiari, Luca [Centre for Antimatter-Matter Studies, School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide 5001, South Australia (Australia); Machacek, J. R.; Anderson, Emma; Sullivan, James P. [Centre for Antimatter-Matter Studies, Research School of Physics and Engineering, The Australian National University, Canberra, ACT 0200 (Australia); White, Ron D. [Centre for Antimatter-Matter Studies, School of Engineering and Physical Sciences, James Cook University, Townsville, 4810 Queensland (Australia); Brunger, M. J. [Centre for Antimatter-Matter Studies, School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide 5001, South Australia (Australia); Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia); Buckman, Stephen J. [Centre for Antimatter-Matter Studies, Research School of Physics and Engineering, The Australian National University, Canberra, ACT 0200 (Australia); Institute of Mathematical Sciences, University of Malaya, 50603 Kuala Lumpur (Malaysia); Garcia, Gustavo [Instituto de Fısica Fundamental, Consejo Superior de Investigationes Cientıficas (CSIC), Serrano 113-bis, E-28006 Madrid (Spain); Blanco, Francisco [Departamento de Fısica Atomica, Molecular y Nuclear, Universidad Complutense de Madrid, E-28040 Madrid (Spain)

    2014-01-28

    Utilising a high-resolution, trap-based positron beam, we have measured both elastic and inelastic scattering of positrons from water vapour. The measurements comprise differential elastic, total elastic, and total inelastic (not including positronium formation) absolute cross sections. The energy range investigated is from 1 eV to 60 eV. Comparison with theory is made with both R-Matrix and distorted wave calculations, and with our own application of the Independent Atom Model for positron interactions.

  3. Positron interactions with water-total elastic, total inelastic, and elastic differential cross section measurements.

    Science.gov (United States)

    Tattersall, Wade; Chiari, Luca; Machacek, J R; Anderson, Emma; White, Ron D; Brunger, M J; Buckman, Stephen J; Garcia, Gustavo; Blanco, Francisco; Sullivan, James P

    2014-01-28

    Utilising a high-resolution, trap-based positron beam, we have measured both elastic and inelastic scattering of positrons from water vapour. The measurements comprise differential elastic, total elastic, and total inelastic (not including positronium formation) absolute cross sections. The energy range investigated is from 1 eV to 60 eV. Comparison with theory is made with both R-Matrix and distorted wave calculations, and with our own application of the Independent Atom Model for positron interactions.

  4. Single-incision total laparoscopic hysterectomy

    Directory of Open Access Journals (Sweden)

    Sinha Rakesh

    2011-01-01

    Full Text Available Single-incision laparoscopic surgery is an alternative to conventional multiport laparoscopy. Single-access laparoscopy using a transumbilical port affords maximum cosmetic benefits because the surgical incision is hidden in the umbilicus. The advantages of single-access laparoscopic surgery may include less bleeding, infection, and hernia formation and better cosmetic outcome and less pain. The disadvantages and limitations include longer surgery time, difficulty in learning the technique, and the need for specialized instruments. Ongoing refinement of the surgical technique and instrumentation is likely to expand its role in gynecologic surgery in the future. We perform single-incision total laparoscopic hysterectomy using three ports in the single transumbilical incision.

  5. Potential Modulation on Total Internal Reflection Ellipsometry.

    Science.gov (United States)

    Liu, Wei; Niu, Yu; Viana, A S; Correia, Jorge P; Jin, Gang

    2016-03-15

    Electrochemical-total internal reflection ellipsometry (EC-TIRE) has been proposed as a technique to observe the redox reactions on the electrode surface due to its high phase sensitivity to the electrolyte/electrode interface. In this paper, we mainly focus on the influence of the potential modulation on the TIRE response. The analysis suggests that both dielectric constant variation of gold and the electric double layer transformation would modulate the reflection polarization of the surface. For a nonfaradaic process, the signal of TIRE would be proportional to the potential modulation. To testify the analysis, linear sweep voltammetry and open circuit measurement have been performed. The results strongly support the system analysis. PMID:26889871

  6. Aggregated Total Internal Reflection Optics for Solar

    Science.gov (United States)

    Schultz, David; Grimmer, Chris; Fine, Kevin; Evans, Matt; Ghosh, Shondip

    2010-10-01

    An agglomeration of factors has stifled the economic promise of CPV. Foremost among these factors are: insufficient optical efficiency, misfit with existing solar infrastructure, high costs, and inadequate reliability of the optic-receiver package. These difficulties are significantly driven by the choice of optic. The CPV industry is constrained in a paradigm of bulky reflective or refractive optics that operate best at either low concentration (2-5x) or high concentration (100x and above). Low concentration approaches are plagued by marginal economics, while high concentration approaches face technical risks and do not fit well with the existing solar infrastructure. Using total internal reflection as the primary optical mechanism, a cost effective, line-focus optic can be produced at scale to provide superior optical performance in a flat profile and operate at a mid level of concentration to optimize the tradeoff between economic benefit and adoptability.

  7. STUDY ON TOTAL SEDIMENT TRANSPORT BY FLOW

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Total sediment transport under the action of flow includes generally three forms of sediment transport, suspended load, density current and bed load. How to realize simultaneously these three forms of sediment movement in an identical physical model was studied in this paper. For the suspended load, fall and pickup similarities were used to design sediment gradation, and similarities of sediment-carrying capacity and scouring and depositing time were be insured. For the density current its occurrence condition should be similar, and similarities of sediment concentration and depositing time were insured. For the bed load, sediment gradation was designed by the similarity of incipient motion, and similarities of sediment discharge and scouring and depositing time were satisfied. And a physical model test was conducted.

  8. THE MAIN PRINCIPLES OF TOTAL QUALITY MANAGEMENT

    Directory of Open Access Journals (Sweden)

    Andrei DIAMANDESCU

    2016-06-01

    Full Text Available Nowadays the industry is one of the main economic sectors, with a major contribution to achieving and maintaining a high rate of economic growth. The processing industry operation to high economic performance requires changes in structural terms, the re-engineering of processes and management. In this regard, one of the main actions taken at the level of companies in the manufacturing industry is the implementation of quality systems. Practicing quality management system not only allows businesses to react to changes taking place in business, but also to inflict them by the controlling of the future. This paper aims to analyze the principles of Total Quality Management – TQM and will highlight the advantages that organizations could obtain by applying each principle separately in the process of management.

  9. Segmental blood pressure after total hip replacement

    DEFF Research Database (Denmark)

    Gebuhr, Peter Henrik; Soelberg, M; Henriksen, Jens Henrik

    1992-01-01

    Twenty-nine patients due to have a total hip replacement had their systemic systolic and segmental blood pressures measured prior to operation and 1 and 6 weeks postoperatively. No patients had signs of ischemia. The segmental blood pressure was measured at the ankle and at the toes. A significant...... on the operated side. None of the patients had symptoms from the lowered pressure. We conclude that in patients without signs of ischemia, the postoperative segmental pressure decrease is reversible and therefore not dangerous....... drop was found in all pressures 1 week postoperatively. The decrease followed the systemic pressure and was restored to normal after 6 weeks. In a group of six patients with preoperatively decreased ankle pressure, a significant transient further decrease in the ankle-toe gradient pressure was found...

  10. Neck after total laryngectomy: CT study

    Energy Technology Data Exchange (ETDEWEB)

    DiSantis, D.J.; Balfe, D.M.; Hayden, R.E.; Sagel, S.S.; Sessions, D.; Lee, J.K.T.

    1984-12-01

    Computed tomographic scans in 23 patients who had undergone total laryngectomy were analyzed retrospectively to determine normal postoperative appearance and to evaluate the role of CT in assessing recurrent neoplasm. Nine patients without clinical evidence of recurrence illustrated the normal postoperative changes: a round or ovoid neopharynx connecting the base of the tongue with the cervical esophagus and intact fat planes surrounding the neopharynx, neurovascular bundles, and sternocleidomastoid muscles. In the 12 patients with recurrent neoplasm, the CT manifestations included masses involving the internal jugular lymph node chain, tracheostomy site, or paratracheal region. CT supplemented physical examination and indirect mirror examination, providing data regarding presence and extent of recurrent tumor and aiding in planning the mode and scope of therapy.

  11. Total Mercury in Six Antarctic Notothenioid Fishes.

    Science.gov (United States)

    Wintle, Nathan J P; Sleadd, Isaac M; Gundersen, Deke T; Kohl, Kristina; Buckley, Bradley A

    2015-11-01

    We analyzed white muscle samples from six species of Antarctic fish (suborder Notothenioidei) collected in 2011 from McMurdo Sound, Ross Sea, Antarctica, to assess levels of total mercury (THg). Gymnodraco acuticeps and Trematomus bernacchii exhibited the highest concentrations of THg followed by Trematomus pennellii, Trematomus nicolai, Trematomus newnesi and Pagothenia borchgrevinki, (71.3, 53.9±32.1, 45.8±27.3, 37.2±18.6, 35.7±23.6, and 21.9±2.8 ng/g wet weight, respectively). The results from this study suggest that THg has the potential to bioaccumulate from various marine Antarctic ecosystems into biota.

  12. Enantioselective Total Synthesis of (-)-Alstoscholarisine A.

    Science.gov (United States)

    Liang, Xiao; Jiang, Shi-Zhi; Wei, Kun; Yang, Yu-Rong

    2016-03-01

    We report a concise and highly enantioselective total synthesis of (-)-alstoscholarisine A (1), a recently isolated monoterpenoid indole alkaloid that has significant bioactivity in promoting adult neuronal stem cells proliferation. A highly enantioselective (99% ee), intramolecular Ir-catalyzed Friedel-Crafts alkylation of indole 9 with a secondary allylic alcohol was utilized to establish the first stereogenic center upon which the other three contiguous chiral centers were readily set by a highly stereoselective tandem 1,4-addition and aldol reaction. The key tetrahydropyran was constructed through a hemiacetal reduction, and the final aminal bridge was forged by a one-pot reductive amination/cyclization. The conciseness of this approach was highlighted by building core bonds in each step with a minimalist protecting group strategy. PMID:26882407

  13. Modeling total expenditure on warranty claims

    CERN Document Server

    Mitra, Abhimanyu

    2010-01-01

    We approximate the distribution of total expenditure of a retail company over warranty claims incurred in a fixed period [0, T], say the following quarter. We consider two kinds of warranty policies, namely, the non-renewing free replacement warranty policy and the non-renewing pro-rata warranty policy. Our approximation holds under modest assumptions on the distribution of the sales process of the warranted item and the nature of arrivals of warranty claims. We propose a method of using historical data to statistically estimate the parameters of the approximate distribution. Our methodology is applied to the warranty claims data from a large car manufacturer for a single car model and model year.

  14. Total synthesis of diterpenoid steenkrotin A.

    Science.gov (United States)

    Pan, Saiyong; Xuan, Jun; Gao, Beiling; Zhu, An; Ding, Hanfeng

    2015-06-01

    A concise and diastereoselective total synthesis of the diterpenoid (±)-steenkrotin A is described for the first time. The strategy mainly features three key ring formations: 1) a rhodium-catalyzed O-H bond insertion followed by an intramolecular carbonyl-ene reaction to build up the tetrahydrofuran subunit; 2) sequential SmI2 -mediated Ueno-Stork and ketyl-olefin cyclizations to construct the [5,7] spirobicyclic skeleton; and 3) an intramolecular aldol condensation/vinylogous retro-aldol/aldol sequence to form the final six-membered ring with inversion of the relative configuration at the C7 position. PMID:25891977

  15. The Total Synthesis of Inostamycin A.

    Science.gov (United States)

    Yu, Guangri; Jung, Byunghyuck; Lee, Hee-Seung; Kang, Sung Ho

    2016-02-12

    The first total synthesis of inostamycin A is described. With efficient and stereoselective synthetic routes to aldehyde 3 and ketone 4 developed through asymmetric aldol reactions, addition reactions and reduction, and with chiral building blocks, the two large fragments were coupled with remarkable anti stereoselectivity and efficiency by aldol condensation. The coupling reaction provided the complete carbon skeleton with all the requisite functional groups and stereogenic centers for inostamycin A. The two quaternary carbons at C20 and C16 of ketone 4 were elaborated in a highly stereocontrolled manner by addition reactions of the transmetallated 5 to ethyl ketone 6 and the transmetallated 7 to methyl ketone 8, respectively, in which the use of LaCl3 for transmetallation was critical for high coupling efficiency. PMID:26800259

  16. Space orientation of total hip prosthesis

    International Nuclear Information System (INIS)

    A method for in vivo determination of orientation and relation in space of components of total hip prosthesis is described. The method allows for determination of the orientation of the prosthetic components in well defined anatomic planes of the body. Furthermore the range of free motion from neutral position to the point of contact between the edge of the acetabular opening and the neck of the femoral component can be determined in various directions. To assess the accuracy of the calculations a phantom prosthesis was studied in nine different positions and the measurements of the space oriented parameters according to the present method correlated to measurements of the same parameters according to Selvik's stereophotogrammetric method. Good correlation ws found. The role of prosthetic malpositioning and component interaction evaluated with the present method in the development of prosthetic loosening and displacement is discussed. (orig.)

  17. Tissue air ratio in total body irradiation

    International Nuclear Information System (INIS)

    On the basis of dose readings in 102 patients treated with total body irradiation (TBI), a 'tissue air ratio (TAR) curve' has been produced. It could be useful to precalculate treatment time in TBI, for dose prescription to a specific point, provided the same source (60Co) and treatment setting (lateral irradiation; 3 m source-axis distance; reference point at thighs bifurcation, neat the perineum) is used. The TAR curve produced, and the formula relating tissue depth to TAR value, are presented, and compared to preexisting data for 'magna fields' treatments. This curve is exponential, and in semilog representation becomes straight, as every classic TAR curve; it is lower than others, reflecting non full-scatter situation in patient irradiation. (orig.)

  18. Total chemical management in photographic processing

    Science.gov (United States)

    Luden, Charles; Schultz, Ronald

    1985-01-01

    The mission of the U. S. Geological Survey's Earth Resources Observation Systems (EROS) Data Center is to produce high-quality photographs of the earth taken from aircraft and Landsat satellite. In order to meet the criteria of producing research-quality photographs, while at the same time meeting strict environmental restrictions, a total photographic chemical management system was installed. This involved a three-part operation consisting of the design of a modern chemical analysis laboratory, the implementation of a chemical regeneration system, and the installation of a waste treatment system, including in-plant pretreatment and outside secondary waste treatment. Over the last ten years the result of this program has yielded high-quality photographs while saving approximately 30,000 per year and meeting all Environmental Protection Agency (EPA) restrictions.

  19. Implant survival after total elbow arthroplasty

    DEFF Research Database (Denmark)

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

    2014-01-01

    in 234 patients at a mean follow-up of 8.7 years (range, 0-27 years). The overall 5-year survival was 90% (95% confidence interval [CI], 88%-94%), and 10-year survival was 81% (95% CI, 76%-86%). TEAs performed with the unlinked design had a relative risk of revision of 1.9 (95% CI, 1.1-3.2) compared......BACKGROUND: Total elbow arthroplasty (TEA) is an established treatment for late-stage arthritis of the elbow. Indications have expanded to osteoarthritis and nonunion in distal humeral fractures. Information on implant survival and risk factors for revision is still sparse. The aim of this study...... was to evaluate implant survival and risk factors for revision of TEAs inserted in patients in the eastern part of Denmark in the period from 1980 until 2008. MATERIAL AND METHODS: The Danish National Patient Register provided personal identification numbers for patients who underwent TEA procedures from 1980...

  20. Pathology of Coronary Chronic Total Occlusion

    Directory of Open Access Journals (Sweden)

    Kenichi Sakakura

    2016-06-01

    Full Text Available There is an increasing need for percutaneous revascularization procedures of coronary Chronic Total Occlusion (CTO, because many patients with severe coronary artery disease have limited options for revascularization. Although the success rate of percutaneous revascularization of CTOs was unsatisfactory from the 1990s to the 2000s, recent technological advances in interventional strategies have improved the success rate to 85%. Detailed histological assessment of human autopsy studies of CTO has contributed significantly to the refinement in Percutaneous Coronary Intervention (PCI techniques and device development. We have recently reported the pathological findings and characteristics of CTOs that occur in different clinical scenarios. In this review, we discuss the pathology of CTOs to facilitate greater understanding of revascularization strategies for CTOs.