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Sample records for benzyne-furan cycloadditions total

  1. Catalysis of Heterocyclic Azadiene Cycloaddition Reactions by Solvent Hydrogen Bonding: Concise Total Synthesis of Methoxatin.

    Science.gov (United States)

    Glinkerman, Christopher M; Boger, Dale L

    2016-09-28

    Although it has been examined for decades, no general approach to catalysis of the inverse electron demand Diels-Alder reactions of heterocyclic azadienes has been introduced. Typically, additives such as Lewis acids lead to nonproductive consumption of the electron-rich dienophiles without productive activation of the electron-deficient heterocyclic azadienes. Herein, we report the first general method for catalysis of such cycloaddition reactions by using solvent hydrogen bonding of non-nucleophilic perfluoroalcohols, including hexafluoroisopropanol (HFIP) and trifluoroethanol (TFE), to activate the electron-deficient heterocyclic azadienes. Its use in promoting the cycloaddition of 1,2,3-triazine 4 with enamine 3 as the key step of a concise total synthesis of methoxatin is described.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-22

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

  3. Intramolecular Cycloaddition of Imines of Cysteine Derivatives

    Directory of Open Access Journals (Sweden)

    Teresa M. V. D. Pinho e Melo

    1998-02-01

    Full Text Available Azomethine ylides were generated from Schiffs bases of S-allylcysteine methyl ester and their intramolecular 1,3-dipolar cycloadditions were studied. These reactions led to the synthesis of thieno[3,4-b]pyrrole derivatives in good yield.

  4. 18F-Labeling Using Click Cycloadditions

    Directory of Open Access Journals (Sweden)

    Kathrin Kettenbach

    2014-01-01

    Full Text Available Due to expanding applications of positron emission tomography (PET there is a demand for developing new techniques to introduce fluorine-18 (t1/2=109.8 min. Considering that most novel PET tracers are sensitive biomolecules and that direct introduction of fluorine-18 often needs harsh conditions, the insertion of 18F in those molecules poses an exceeding challenge. Two major challenges during 18F-labeling are a regioselective introduction and a fast and high yielding way under mild conditions. Furthermore, attention has to be paid to functionalities, which are usually present in complex structures of the target molecule. The Cu-catalyzed azide-alkyne cycloaddition (CuAAC and several copper-free click reactions represent such methods for radiolabeling of sensitive molecules under the above-mentioned criteria. This minireview will provide a quick overview about the development of novel 18F-labeled prosthetic groups for click cycloadditions and will summarize recent trends in copper-catalyzed and copper-free click 18F-cycloadditions.

  5. Enatioselective[2+2+2] Cycloaddition as A Synthetic Tool

    Institute of Scientific and Technical Information of China (English)

    T.Shibata; S.Yoshida; M.Otsuka; Y.Arai; K.Endo

    2007-01-01

    1 Results Transition metal-catalyzed [2+2+2] cycloaddition is one of the most efficient protocols for the construction of six-membered ring system.Our group has comprehensively studied various types of highly enantioselective [2+2+2] cycloaddition for the synthesis of chiral cycloadducts; we already reported an iridium-catalyzed intermolecular [2+2+2] cycloaddition between α,ω-diynes,having various tethers and substituents on the alkyne termini,and monoalkynes,possessing oxygen or/and nitrogen functiona...

  6. 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.

  7. Neutral Diboron Analogues of Archetypal Aromatic Species by Spontaneous Cycloaddition.

    Science.gov (United States)

    Arrowsmith, Merle; Böhnke, Julian; Braunschweig, Holger; Celik, Mehmet Ali; Claes, Christina; Ewing, William C; Krummenacher, Ivo; Lubitz, Katharina; Schneider, Christoph

    2016-09-05

    Among the numerous routes organic chemists have developed to synthesize benzene derivatives and heteroaromatic compounds, transition-metal-catalyzed cycloaddition reactions are the most elegant. In contrast, cycloaddition reactions of heavier alkene and alkyne analogues, though limited in scope, proceed uncatalyzed. In this work we present the first spontaneous cycloaddition reactions of lighter alkene and alkyne analogues. Selective addition of unactivated alkynes to boron-boron multiple bonds under ambient conditions yielded diborocarbon equivalents of simple aromatic hydrocarbons, including the first neutral 6 π-aromatic diborabenzene compound, a 2 π-aromatic triplet biradical 1,3-diborete, and a phosphine-stabilized 2 π-homoaromatic 1,3-dihydro-1,3-diborete. DFT calculations suggest that all three compounds are aromatic and show frontier molecular orbitals matching those of the related aromatic hydrocarbons, C6 H6 and C4 H4 (2+) , and homoaromatic C4 H5 (+) .

  8. 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.

  9. 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

  10. Copper-catalyzed azide alkyne cycloaddition polymer networks

    Science.gov (United States)

    Alzahrani, Abeer Ahmed

    -CuAAC reaction and a chain-growth acrylate homopolymerization were demonstrated and used to form branched polymer structures. A bulk, organic soluble initiation system consisting of a Cu(II) salt and a primary amine was also examined in both model reactions and in bulk polymerizations. The system was shown to be highly efficient, leading to nearly complete CuAAC polymerization at ambient temperature. Increasing the ratio of amine to copper from 1 to 4 increases the CuAAC reaction rate significantly from 4 mM/min for 1:1 ratio of Cu(II):hexyalmine to 14mM/min for 1:4 ratio. The concentration dependence of the amine on the reaction rate enables the polymerization rate to be controlled simply by manipulating the hexylamine concentration. Sequential thiol--acrylate and photo-CuAAC click reactions were utilized to form two-stage reactive polymer networks capable of generating wrinkles in a facile manner. The click thiol-Michael addition reaction was utilized to form a cross-linked polymer with residual, reactive alkyne sites that remained tethered throughout the network. The latent, unreacted alkyne sites are subsequently reacted with diazide monomers via a photoinduced Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction to increase the cross-link density. Increased cross-linking raised the modulus and glass transition temperature from 1.6 MPa and 2 °C after the thiol-acrylate reaction to 4.4 MPa and 22 °C after the CuAAC reaction, respectively. The double click reaction approach led to micro-wrinkles with well-controlled wavelength and amplitude of 8.50 +/- 1.6 and 1.4 μm, respectively, for a polymer with a 1280 μm total film thickness. Additionally, this approach further enables spatial selectivity of wrinkle formation by photo-patterning. The CuAAC-based polymerization was also used to design smart, responsive porous materials from well-defined CuAAC networks, which possesses a high glass transition temperature (Tg= 115°C) due to the formation of the triazole linkages

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

    Directory of Open Access Journals (Sweden)

    Peter Ertl

    1997-04-01

    Full Text Available The cycloaddition of the chiral nitrile oxide 1 to 1-R-substituted 3,3-methylene-5,5-dimethyl-2-pyrrolidinones 2 (where R is H, n-butyl-, 1,1-dimethylethoxycarbonyl-, 1-methylethenyl- and acetyl- proceeds regioselectively under the formation of spiroisoxazolines, namely 7-R-substituted-6-oxo-8,8-dimethyl-1-oxa-2,7-diazaspiro[4,4]non-2-enes 5 and 6. The asymmetric induction expected by the a-chiral centre of the nitrile oxide 1 was not very effective, diastereoisomers 5 and 6 were formed in an approximate 50:50 ratio. The stereoselectivity of the 1,3-dipolar cycloaddition of the arylnitrile oxide 7 with the chiral lactam 3 and the achiral lactone 4 are investigated. The attack of the 1,3-dipole occurred from the less hindered face of the dipolarophile 3 and 4, giving the major isomer 8 and 10, respectively.

  12. Halo substituent effects on intramolecular cycloadditions involving furanyl amides.

    Science.gov (United States)

    Padwa, Albert; Crawford, Kenneth R; Straub, Christopher S; Pieniazek, Susan N; Houk, K N

    2006-07-21

    Intramolecular Diels-Alder reactions involving a series of N-alkenyl-substituted furanyl amides were investigated. Stable functionalized oxanorbornenes were formed in high yield upon heating at 80-110 degrees C. The cycloaddition reactions include several bromo-substituted furanyl amides, and these systems were found to proceed at a much faster rate and in higher yield than without substitution. This effect was observed by incorporating a halogen in the 3- or 5-position of the furan ring and appears to be general. The origin of increased cycloaddition rates for halo-substituted furans has been investigated with quantum mechanical calculations. The success of these reactions is attributed to increases in reaction exothermicities; this both decreases activation enthalpies and increases barriers to retrocycloadditions. Halogen substitution on furan increases reactant energy and stabilizes the product, which is attributed to the preference of electronegative halogens to be attached to a more highly alkylated and therefore more electropositive framework.

  13. Direct Evidence of a Dinuclear Copper Intermediate in Cu(I)-Catalyzed Azide–Alkyne Cycloadditions

    OpenAIRE

    Worrell, B. T.; Malik, J.A.; FOKIN, V.V.

    2013-01-01

    The copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) has become a commonly employed method for the synthesis of complex molecular architectures under challenging conditions. Despite the widespread use of copper-catalyzed cycloaddition reactions, the mechanism of these processes has remained difficult to establish due to the involvement of multiple equilibria between several reactive intermediates. Real-time monitoring of a representative cycloaddition process via heat flow reaction calo...

  14. 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.

  15. 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.

  16. Regioselective de novo synthesis of cyanohydroxypyridines with a concerted cycloaddition mechanism.

    Science.gov (United States)

    Lu, Jin-Yong; Keith, John A; Shen, Wei-Zheng; Schürmann, Markus; Preut, Hans; Jacob, Timo; Arndt, Hans-Dieter

    2008-10-08

    An efficient cycloaddition reaction of 1-alkoxy-1-azadienes with alpha,alpha-dicyanoalkenes is described, which gives facile access to highly substituted 3-hydroxypyridines in very good yields and with complete regiocontrol and chemoselectivity. The reaction path was investigated in detail by quantum mechanics calculations, reporting that a concerted cycloaddition mechanism and thermodynamic control synergistically contribute to the observed selectivity.

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

    Science.gov (United States)

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

    2016-05-19

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

  18. Reactivity and Chemoselectivity of Allenes in Rh(I)-Catalyzed Intermolecular (5 + 2) Cycloadditions with Vinylcyclopropanes: Allene-Mediated Rhodacycle Formation Can Poison Rh(I)-Catalyzed Cycloadditions

    Science.gov (United States)

    2015-01-01

    Allenes are important 2π building blocks in organic synthesis and engage as 2-carbon components in many metal-catalyzed reactions. Wender and co-workers discovered that methyl substituents on the terminal allene double bond counterintuitively change the reactivities of allenes in [Rh(CO)2Cl]2-catalyzed intermolecular (5 + 2) cycloadditions with vinylcyclopropanes (VCPs). More sterically encumbered allenes afford higher cycloadduct yields, and such effects are also observed in other Rh(I)-catalyzed intermolecular cycloadditions. Through density functional theory calculations (B3LYP and M06) and experiment, we explored this enigmatic reactivity and selectivity of allenes in [Rh(CO)2Cl]2-catalyzed intermolecular (5 + 2) cycloadditions with VCPs. The apparent low reactivity of terminally unsubstituted allenes is associated with a competing allene dimerization that irreversibly sequesters rhodium. With terminally substituted allenes, steric repulsion between the terminal substituents significantly increases the barrier of allene dimerization while the barrier of the (5 + 2) cycloaddition is not affected, and thus the cycloaddition prevails. Computation has also revealed the origin of chemoselectivity in (5 + 2) cycloadditions with allene-ynes. Although simple allene and acetylene have similar reaction barriers, intermolecular (5 + 2) cycloadditions of allene-ynes occur exclusively at the terminal allene double bond. The terminal double bond is more reactive due to the enhanced d−π* backdonation. At the same time, insertion of the internal double bond of an allene-yne has a higher barrier as it would break π conjugation. Substituted alkynes are more difficult to insert compared with acetylene, because of the steric repulsion from the additional substituents. This leads to the greater reactivity of the allene double bond relative to the alkynyl group in allene-ynes. PMID:25379606

  19. Synthesis of heterocycles by formal cycloadditions of isocyanides.

    Science.gov (United States)

    Kruithof, Art; Ruijter, Eelco; Orru, Romano V A

    2015-03-01

    Synthetic methodology for the synthesis of heterocycles is of continuous and high interest with applications in materials, catalysis, and medicines. Multicomponent reactions are suitable tools to efficiently generate chemically diverse sets of heterocycles with sufficient structural complexity. Especially isocyanides have proven to be particularly versatile building blocks in these one-pot processes. Due to their electronic structure, isocyanides are able to act sequentially or simultaneously as a nucleophile and an electrophile. Traditionally, isocyanides are therefore frequently used in multicomponent chemistry. In the recent literature, numerous reactions have been reported that involve formal cycloadditions of isocyanides with conjugated heterodienes. This Focus Review aims at mapping this reactivity and at providing insight into the relationship between the various reported reaction partners and the observed reactivity modes.

  20. Cycloadditions of 2-azaallyllithium species with conjugated polyenes.

    Science.gov (United States)

    Pearson, William H; Mans, Douglas M; Kampf, Jeff W

    2004-02-20

    2-Azaallyllithium species [R(1)CH(-)N=C(X)R(2)Li(+), where R(1) and R(2) are alkyl and X = OMe] were generated by tin-lithium exchange of (2-azaallyl)stannanes and underwent [pi4s+pi2s] and [pi6s+pi4s] cycloadditions with cyclic dienes and trienes, respectively, to generate novel bridged azabicyclic compounds in a highly diastereoselective endo fashion. The periselectivity using cycloheptatriene was modest, producing a 1:1 mixture of [pi6s+pi4s] and [pi4s+pi2s] adducts. The reactions of 2-azaallyllithium species with dienes proceeded by a [pi4s+pi2s] pathway. The cycloadducts derived from cyclic 2-azaallyllithium species possess the 7-azabicyclo[2.2.1]heptane (tropane) or 8-azabicyclo[3.2.1]octane ring system and have been elaborated into cocaine-like analogues.

  1. Advanced hybrid fluoropolymers from the cycloaddition of aryl trifluorovinyl ethers

    Science.gov (United States)

    Ligon, S. Clark, Jr.

    This dissertation discusses the synthesis of aryl trifluorovinyl ethers and their cycloaddition polymerization to give perfluorocyclobutyl (PFCB) polymers. To explore the stereochemistry of these polymers, simple monomfunctional aryl trifluorovinyl ethers were dimerized and the resultant cis and trans isomers were separated. Differences in structure help to improve understanding of the amorphous nature of the bulk PFCB polymeric material. To apply this knowledge, crown ether containing perfluorocyclobutyl (PFCB) polymers were synthesized for use in lithium ion battery applications. While poor solubility has hindered further development of these materials, slight modifications to structure may provide a solution. Also described is a fluorinated aryl vinyl ether and its attempted copolymerization with chlorotrifluoroethylene. While this copolymerization did not yield the desired materials, novel semifluorinated phenol precursors have been utilized in reactions with carboxylic acids to give polyesters and most recently with phosgene like species to give polycarbonates. Next, PFCB polymers were post functionalized with fluoroalkyl tethers to improve oleophobicity and hydrophobicity without decreasing thermal stability or optical clarity. In addition, various silica nanostructures were functionalized with aryl trifluorovinyl ethers. This includes the reaction of aryl silanes to give trifluorovinyl ether functional POSS and their polymerization to provide PFCB hybrid materials. Silane coupling agents were also used to functionalize colloidal silica and fumed silica nanoparticles. These procedures allow excellent dispersion of the silica nanoparticles throughout the fluoropolymer matrix. Finally, the reaction of aryl trifluorovinyl ether with nonfluorinated alkenes and alkynes was explored. In these reactions, the fluorinated olefin adds with the hydrocarbon olefin to give semifluorinated cyclobutanes (SFCB) and with the alkyne to give semifluorinated cyclobutene. The

  2. 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

  3. The Copper-nicotinamide complex: sustainable applications in coupling and cycloaddition reactions

    Science.gov (United States)

    Crystalline copper (II)-nicotinamide complex, synthesized via simple mixing of copper chloride and nicotinamide solution at room temperature, catalyzes the C-S, C-N bond forming and cycloaddition reactions under a variety of sustainable reaction conditions.

  4. 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.

  5. Synthesis of 2H-indazoles by the [3 + 2] cycloaddition of arynes and sydnones.

    Science.gov (United States)

    Wu, Chunrui; Fang, Yuesi; Larock, Richard C; Shi, Feng

    2010-05-21

    A rapid and efficient synthesis of 2H-indazoles has been developed, which involves the [3 + 2] dipolar cycloaddition of arynes and sydnones. The process proceeds under mild reaction conditions in good to excellent yields.

  6. 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.

  7. Theoretical studies of excited state 1,3 dipolar cycloadditions

    Science.gov (United States)

    Belluccci, Michael A.

    The 1,3 dipolar photocycloaddition reaction between 3-hydroxy-4',5,7-trimethoxyflavone (3-HTMF) and methyl cinnamate is investigated in this work. Since its inception in 2004 [JACS, 124, 13260 (2004)], this reaction remains at the forefront in the synthetic design of the rocaglamide natural products. The reaction is multi-faceted in that it involves multiple excited states and is contingent upon excited state intramolecular proton transfer (ESIPT) in 3-HTMF. Given the complexity of the reaction, there remain many questions regarding the underlying mechanism. Consequently, throughout this work we investigate the mechanism of the reaction along with a number of other properties that directly influence it. To investigate the photocycloaddition reaction, we began by studying the effects of different solvent environments on the ESIPT reaction in 3-hydroxyflavone since this underlying reaction is sensitive to the solvent environment and directly influences the cycloaddition. To study the ESIPT reaction, we developed a parallel multi-level genetic program to fit accurate empirical valence bond (EVB) potentials to ab initio data. We found that simulations with our EVB potentials accurately reproduced experimentally determined reaction rates, fluorescence spectra, and vibrational frequency spectra in all solvents. Furthermore, we found that the ultrafast ESIPT process results from a combination of ballistic transfer and intramolecular vibrational redistribution. To investigate the cycloaddition reaction mechanism, we utilized the string method to obtain minimum energy paths on the ab initio potential. These calculations demonstrated that the reaction can proceed through formation of an exciplex in the S1 state, followed by a non-adiabatic transition to the ground state. In addition, we investigated the enantioselective catalysis of the reaction using alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolan-4,5-dimethanol alcohol (TADDOL). We found that TADDOL lowered the energy

  8. 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.

  9. 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.

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

    Science.gov (United States)

    Mendes, Desiree E.; Schoffstall, Allen M.

    2011-01-01

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

  11. Electrochemically protected copper(I)-catalyzed azide-alkyne cycloaddition.

    Science.gov (United States)

    Hong, Vu; Udit, Andrew K; Evans, Richard A; Finn, M G

    2008-06-16

    The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction has found broad application in myriad fields. For the most demanding applications that require high yields at low substrate concentrations, highly active but air-sensitive copper complexes must be used. We describe here the use of an electrochemical potential to maintain catalysts in the active Cu(I) oxidation state in the presence of air. This simple procedure efficiently achieves excellent yields of CuAAC products from both small-molecule and protein substrates without the use of potentially damaging chemical reducing agents. A new water-soluble carboxylated version of the popular tris(benzyltriazolylmethyl)amine (TBTA) ligand is also described. Cyclic voltammetry revealed reversible or quasi-reversible electrochemical redox behavior of copper complexes of the TBTA derivative (2; E(1/2)=60 mV vs. Ag/AgCl), sulfonated bathophenanthroline (3; E(1/2)=-60 mV), and sulfonated tris(benzimidazoylmethyl)amine (4; E(1/2) approximately -70 mV), and showed catalytic turnover to be rapid relative to the voltammetry time scale. Under the influence of a -200 mV potential that was established by using a reticulated vitreous carbon working electrode, CuSO4 and 3 formed a superior catalyst. Electrochemically protected bioconjugations in air were performed by using bacteriophage Qbeta that was derivatized with azide moieties at surface lysine residues. Complete derivatization of more than 600 reactive sites per particle was demonstrated within 12 h of electrolysis with substoichiometric quantities of Cu3.

  12. 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

  13. Application of cycloaddition reactions to the syntheses of novel boron compounds.

    Science.gov (United States)

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

    2010-12-21

    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.

  14. 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.

  15. [2+2+2] Cycloaddition Reactions of Macrocyclic Systems Catalyzed by Transition Metals. A Review

    Directory of Open Access Journals (Sweden)

    Anna Roglans

    2010-12-01

    Full Text Available Polyalkyne and enediyne azamacrocycles are prepared from arenesulfonamides and various alkyne and alkene derivatives either under basic or neutral conditions. The new family of macrocyclic substrates is tested in the [2+2+2] cycloaddition reaction. Several catalysts are used for the cycloisomerization reaction, and their enantioinduction is evaluated as appropriate. The effect of the structural features of the macrocycles, namely the ring size, substituents in precise positions and the number and type of unsaturations, on the [2+2+2] cycloaddition reaction has also been studied.

  16. 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.

  17. A kinetic study of 1,3-dipolar cycloadditions in micellar media

    NARCIS (Netherlands)

    Rispens, T; Engberts, JBFN

    2003-01-01

    The kinetics of the 1,3-dipolar cycloadditions (DC) of benzonitrile oxide with a series of N-substituted maleimides in micellar media have been investigated. Surfactants studied include anionic sodium dodecyl sulfate, cationic cetyltrimethylammonium bromide, and a series of nonionic alkyl poly(ethyl

  18. 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.

  19. 1,3-DIPOLAR CYCLOADDITION OF PHENYL AZIDE TO NORBORNENE IN AQUEOUS-SOLUTIONS

    NARCIS (Netherlands)

    Wijnen, J.W; Steiner, R.A.; Engberts, J.B.F.N.

    1995-01-01

    Second-order rate constants for the cycloaddition of phenyl azide to norbornene were determined in aqueous solutions. In organic solvents this reaction shows a very small solvent effect. In highly aqueous media, however, remarkable accelerations are observed. The solvent dependence of the rate const

  20. Kinetic solvent effects on 1,3-dipolar cycloadditions of benzonitrile oxide

    NARCIS (Netherlands)

    Rispens, T; Engberts, JBFN

    2005-01-01

    The kinetics of 1,3-dipolar cycloadditions of benzonitrile oxide with a series of N-substituted maleimides and with cyclopentene are reported for water, a wide range of organic solvents and binary solvent mixtures. The results indicate the importance of both solvent polarity and specific hydrogen-bo

  1. 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

  2. Synthesis of 2H-indazoles by the [3 + 2] dipolar cycloaddition of sydnones with arynes.

    Science.gov (United States)

    Fang, Yuesi; Wu, Chunrui; Larock, Richard C; Shi, Feng

    2011-11-04

    A rapid and efficient synthesis of 2H-indazoles has been developed using a [3 + 2] dipolar cycloaddition of sydnones and arynes. A series of 2H-indazoles have been prepared in good to excellent yields using this protocol, and subsequent Pd-catalyzed coupling reactions can be applied to the halogenated products to generate a structurally diverse library of indazoles.

  3. 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

  4. Sulfoxide-directed intramolecular [4 + 2] cycloadditions between 2-sulfinyl butadienes and unactivated alkynes.

    Science.gov (United States)

    Fernández de la Pradilla, Roberto; Tortosa, Mariola; Castellanos, Esther; Viso, Alma; Baile, Raquel

    2010-03-05

    Sulfinyl dienynes undergo thermal and catalyzed IMDA cycloadditions, often at room temperature, to produce cyclohexa-1,4-dienes with good yields and high selectivities. Additionally, the products preserve a synthetically useful vinyl sulfoxide functionality. The selective manipulation of the double bonds in the cycloadducts has also been examined in this work.

  5. Pseudo-bimolecular [2+2] cycloaddition studied by time-resolved photoelectron spectroscopy

    DEFF Research Database (Denmark)

    Brogaard, Rasmus Y; Boguslavskiy, Andrey E; Schalk, Oliver

    2011-01-01

    The first study of pseudo-bimolecular cycloaddition reaction dynamics in the gas phase is presented. We used femtosecond time-resolved photoelectron spectroscopy (TRPES) to study the [2+2] photocycloaddition in the model system pseudo-gem-divinyl[2.2]paracyclophane. From X-ray crystal diffraction...

  6. Construction of Nine-Membered Heterocycles through Palladium-Catalyzed Formal [5+4] Cycloaddition.

    Science.gov (United States)

    Yang, Li-Cheng; Rong, Zi-Qiang; Wang, Ya-Nong; Tan, Zher Yin; Wang, Min; Zhao, Yu

    2017-03-06

    The first catalytic formal [5+4] cycloaddition to prepare nine-membered heterocycles is presented. Under palladium catalysis, the reaction of N-tosyl azadienes and substituted vinylethylene carbonates (VECs) proceeds smoothly to produce benzofuran-fused heterocycles in uniformly high efficiency. Highly diastereoselective functionalization of the nine-membered heterocycles through peripheral attack is also demonstrated.

  7. Synthesis of quinolones by nickel-catalyzed cycloaddition via elimination of nitrile.

    Science.gov (United States)

    Nakai, Kenichiro; Kurahashi, Takuya; Matsubara, Seijiro

    2013-02-15

    Substituted quinolones were efficiently synthesized via the nickel-catalyzed cycloaddition of o-cyanophenylbenzamide derivatives with alkynes. The reaction involves elimination of a nitrile group by cleavage of the two independent aryl-cyano and aryl-carbonyl C-C bonds of the amides.

  8. Thermal and catalytic intramolecular [4+2]-cycloaddition in 2-alkenylfurans

    Energy Technology Data Exchange (ETDEWEB)

    Zubkov, Fedor I; Nikitina, Evgenia V; Varlamov, Alexey V [Department of Physical, Mathematical and Natural Sciences, Peoples' Friendship University of Russia (Russian Federation)

    2005-07-31

    The published data on the intramolecular Diels-Alder reaction in compounds of the 2-alkenylfuran series are generalised. The methods and conditions for the preparation of tricyclic systems are considered. The effects of the substituents in the furan and the unsaturated fragments on the cycloaddition are discussed. The application of this reaction to the synthesis of alkaloids and terpenoids is exemplified.

  9. Pressure-accelerated azide-alkyne cycloaddition: micro capillary versus autoclave reactor performance.

    Science.gov (United States)

    Borukhova, Svetlana; Seeger, Andreas D; Noël, Timothy; Wang, Qi; Busch, Markus; Hessel, Volker

    2015-02-01

    Pressure effects on regioselectivity and yield of cycloaddition reactions have been shown to exist. Nevertheless, high pressure synthetic applications with subsequent benefits in the production of natural products are limited by the general availability of the equipment. In addition, the virtues and limitations of microflow equipment under standard conditions are well established. Herein, we apply novel-process-window (NPWs) principles, such as intensification of intrinsic kinetics of a reaction using high temperature, pressure, and concentration, on azide-alkyne cycloaddition towards synthesis of Rufinamide precursor. We applied three main activation methods (i.e., uncatalyzed batch, uncatalyzed flow, and catalyzed flow) on uncatalyzed and catalyzed azide-alkyne cycloaddition. We compare the performance of two reactors, a specialized autoclave batch reactor for high-pressure operation up to 1800 bar and a capillary flow reactor (up to 400 bar). A differentiated and comprehensive picture is given for the two reactors and the three methods of activation. Reaction speedup and consequent increases in space-time yields is achieved, while the process window for favorable operation to selectively produce Rufinamide precursor in good yields is widened. The best conditions thus determined are applied to several azide-alkyne cycloadditions to widen the scope of the presented methodology.

  10. 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.

  11. 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

  12. Copper-free 'click' : 1,3-dipolar cycloaddition of azides and arynes

    NARCIS (Netherlands)

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

    2008-01-01

    Arynes formed through fluoride-promoted ortho-elimination of o-(trimethylsilyl)aryl triflates can undergo [3 + 2] cycloaddition with various azides to form substituted benzotriazoles. The rapid reaction times and mild conditions make this an attractive variation of the classical 'click' reaction of

  13. 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

  14. Synthesis of pyrroles by consecutive multicomponent reaction/[4 + 1] cycloaddition of alpha-iminonitriles with isocyanides.

    Science.gov (United States)

    Fontaine, Patrice; Masson, Géraldine; Zhu, Jieping

    2009-04-02

    [4 + 1] Cycloaddition of alpha,beta-unsaturated imidoyl cyanide (2-cyano-1-azadienes) with isocyanides in the presence of a catalytic amount of AlCl(3) afforded polysubstituted 2-amino-5-cyanopyrroles in good to excellent yields. In combination with the IBX/TBAB-mediated oxidative Strecker reaction, this important heterocycle is readily synthesized in two steps from simple starting materials.

  15. Quantum Chemistry Study of Cycloaddition Pathways for the Reaction of o-Benzyne with Fullerenes and Carbon Nanotubes

    Science.gov (United States)

    Jaffe, Richard; Han, Jie; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    Functionalization of fullerenes via the [2+2] cycloaddition reaction with o-benzyne has been demonstrated in the laboratory. In contrast, [2+4) cycloaddition products are formed when benzyne reacts with planar polycyclic aromatic hydrocarbons. Using density functional theory (DFT) calculations with Becke's hybrid functional and small contracted gaussian basis sets, we are able to reproduce these product preferences. The objective of this work is to explore the functionalization of carbon nanotubes. We have studied o-benzyne cycloaddition products with a [14,0] single-walled nanotube. We find both the [2+2] and [2+4] adducts to be stable, with the latter product being somewhat favored.

  16. Multicomponent synthesis of spiropyrrolidine analogues derived from vinylindole/indazole by a 1,3-dipolar cycloaddition reaction

    Science.gov (United States)

    Narayanarao, Manjunatha; Koodlur, Lokesh; Revanasiddappa, Vijayakumar G; Gopal, Subramanya

    2016-01-01

    A new series of spiropyrrolidine compounds containing indole/indazole moieties as side chains have been accomplished via a one-pot multicomponent synthesis. The method uses the 1,3-dipolar cycloaddition reaction between N-alkylvinylindole/indazole and azomethine ylides, prepared in situ from cyclic/acyclic amino acids. The 1,3-dipolar cycloaddition proceeds efficiently under thermal conditions to afford the regio- and stereospecific cyclic adducts. PMID:28144362

  17. Multicomponent synthesis of spiropyrrolidine analogues derived from vinylindole/indazole by a 1,3-dipolar cycloaddition reaction

    OpenAIRE

    Narayanarao, Manjunatha; Koodlur, Lokesh; Revanasiddappa, Vijayakumar G; Gopal, Subramanya; KAMILA, Susmita

    2016-01-01

    A new series of spiropyrrolidine compounds containing indole/indazole moieties as side chains have been accomplished via a one-pot multicomponent synthesis. The method uses the 1,3-dipolar cycloaddition reaction between N-alkylvinylindole/indazole and azomethine ylides, prepared in situ from cyclic/acyclic amino acids. The 1,3-dipolar cycloaddition proceeds efficiently under thermal conditions to afford the regio- and stereospecific cyclic adducts.

  18. Multicomponent synthesis of spiropyrrolidine analogues derived from vinylindole/indazole by a 1,3-dipolar cycloaddition reaction.

    Science.gov (United States)

    Narayanarao, Manjunatha; Koodlur, Lokesh; Revanasiddappa, Vijayakumar G; Gopal, Subramanya; Kamila, Susmita

    2016-01-01

    A new series of spiropyrrolidine compounds containing indole/indazole moieties as side chains have been accomplished via a one-pot multicomponent synthesis. The method uses the 1,3-dipolar cycloaddition reaction between N-alkylvinylindole/indazole and azomethine ylides, prepared in situ from cyclic/acyclic amino acids. The 1,3-dipolar cycloaddition proceeds efficiently under thermal conditions to afford the regio- and stereospecific cyclic adducts.

  19. Multicomponent synthesis of spiropyrrolidine analogues derived from vinylindole/indazole by a 1,3-dipolar cycloaddition reaction

    Directory of Open Access Journals (Sweden)

    Manjunatha Narayanarao

    2016-12-01

    Full Text Available A new series of spiropyrrolidine compounds containing indole/indazole moieties as side chains have been accomplished via a one-pot multicomponent synthesis. The method uses the 1,3-dipolar cycloaddition reaction between N-alkylvinylindole/indazole and azomethine ylides, prepared in situ from cyclic/acyclic amino acids. The 1,3-dipolar cycloaddition proceeds efficiently under thermal conditions to afford the regio- and stereospecific cyclic adducts.

  20. Chiral hybrid inorganic-organic materials: synthesis, characterization, and application in stereoselective organocatalytic cycloadditions.

    Science.gov (United States)

    Puglisi, Alessandra; Benaglia, Maurizio; Annunziata, Rita; Chiroli, Valerio; Porta, Riccardo; Gervasini, Antonella

    2013-11-15

    The synthesis of chiral imidazolidinones on mesoporous silica nanoparticles, exploiting two different anchoring sites and two different linkers, is reported. Catalysts 1-4 were prepared starting from l-phenylalanine or l-tyrosine methyl esters and supporting the imidazolidinone onto silica by grafting protocols or azide-alkyne copper(I)-catalyzed cycloaddition. The four catalysts were fully characterized by solid-state NMR, N2 physisorption, SEM, and TGA in order to provide structural assessments, including an evaluation of surface areas, pore dimensions, and catalyst loading. They were used in organocatalyzed Diels-Alder cycloadditions between cyclopentadiene and different aldehydes, affording results comparable to those obtained with the nonsupported catalyst (up to 91% yield and 92% ee in the model reaction between cyclopentadiene and cinnamic aldehyde). The catalysts were recovered from the reaction mixture by simple filtration or centrifugation. The most active catalyst was recycled two times with some loss of catalytic efficiency and a small erosion of ee.

  1. 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.

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

    Science.gov (United States)

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

    2012-12-07

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

  3. The Nitrilimine–Alkene Cycloaddition Regioselectivity Rationalized by Density Functional Theory Reactivity Indices

    Directory of Open Access Journals (Sweden)

    Giorgio Molteni

    2017-01-01

    Full Text Available Conventional frontier molecular orbital theory is not able to satisfactorily explain the regioselectivity outcome of the nitrilimine–alkene cycloaddition. We considered that conceptual density functional theory (DFT could be an effective theoretical framework to rationalize the regioselectivity of the title reaction. Several nitrilimine–alkene cycloadditions were analyzed, for which we could find regioselectivity data in the literature. We computed DFT reactivity indices at the B3LYP/6-311G(2d,p//B3LYP/6-31G(d,p and employed the grand potential stabilization criterion to calculate the preferred regioisomer. Experimental and calculated regioselectivity agree in the vast majority of cases. It was concluded that predominance of a single regioisomer can be obtained by maximizing (i the chemical potential difference between nitrilimine and alkene and (ii the local softness difference between the reactive atomic sites within each reactant. Such maximization can be achieved by carefully selecting the substituents on both reactants.

  4. [4 + 2] cycloadditions of N-alkenyl iminium ions: structurally complex heterocycles from a three-component Diels-Alder reaction sequence.

    Science.gov (United States)

    Sarkar, Nihar; Banerjee, Abhisek; Nelson, Scott G

    2008-07-23

    N-Alkenyl iminium ions serve as conduits to three-component [4 + 2] cycloaddition reactions accessing structurally and stereochemically diverse piperidine derivatives. These cationic 2-azadienes participate in endo- or exo-selective [4 + 2] cycloadditions with electron-rich and neutral alkene dienophiles to generate a tetrahydropyridinium ion as the initial cycloadduct. In situ nucleophilic addition to the cycloaddition-derived iminium ion completes the three-component coupling sequence and affords a versatile synthesis of structurally complex piperidines.

  5. 1,3-Dipolar Cycloaddition in the Preparation of New Fused Heterocyclic Compounds via Thermal Initiation

    Directory of Open Access Journals (Sweden)

    Martin Porubský

    2016-02-01

    Full Text Available This paper describes the synthesis of precursors with a benzo[b]furan skeleton for the intramolecular 1,3-dipolar cycloaddition of azomethine ylides prepared from N-substituted 3-allyl-aminobenzo[b]furan-2-aldehydes and secondary amines derived from α-amino acid esters. Reactions were initiated by heating. The products consisted of four fused rings with three stereogenic centers. Their structure and stereochemistry were determined by NMR spectra and X-ray measurements.

  6. 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...

  7. Intramolecular azide to alkene cycloadditions for the construction of pyrrolobenzodiazepines and azetidino-benzodiazepines.

    Science.gov (United States)

    Hemming, Karl; Chambers, Christopher S; Jamshaid, Faisal; O'Gorman, Paul A

    2014-10-17

    The coupling of proline- and azetidinone-substituted alkenes to 2-azidobenzoic and 2-azidobenzenesulfonic acid gives precursors that undergo intramolecular azide to alkene 1,3-dipolar cycloadditions to give imine-, triazoline- or aziridine-containing pyrrolo[1,4]benzodiazepines (PBDs), pyrrolo[1,2,5]benzothiadiazepines (PBTDs), and azetidino[1,4]benzodiazepines. The imines and aziridines are formed after loss of nitrogen from a triazoline cycloadduct. The PBDs are a potent class of antitumour antibiotics.

  8. Intramolecular Azide to Alkene Cycloadditions for the Construction of Pyrrolobenzodiazepines and Azetidino-Benzodiazepines

    Directory of Open Access Journals (Sweden)

    Karl Hemming

    2014-10-01

    Full Text Available The coupling of proline- and azetidinone-substituted alkenes to 2-azidobenzoic and 2-azidobenzenesulfonic acid gives precursors that undergo intramolecular azide to alkene 1,3-dipolar cycloadditions to give imine-, triazoline- or aziridine-containing pyrrolo[1,4]benzodiazepines (PBDs, pyrrolo[1,2,5]benzothiadiazepines (PBTDs, and azetidino[1,4]benzodiazepines. The imines and aziridines are formed after loss of nitrogen from a triazoline cycloadduct. The PBDs are a potent class of antitumour antibiotics.

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

    Directory of Open Access Journals (Sweden)

    Teruyuki Kondo

    2010-06-01

    Full Text Available A novel rhodium-catalyzed linear codimerization of alkyl phenyl ketenes with internal alkynes to dienones and a novel synthesis of furans by an unusual cycloaddition of diaryl ketenes with internal alkynes have been developed. These reactions proceed smoothly with the same rhodium catalyst, RhCl(PPh33, and are highly dependent on the structure and reactivity of the starting ketenes.

  10. 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)

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

    OpenAIRE

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

    2010-01-01

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

  12. Stereocontrolled cyclic nitrone cycloaddition strategy for the synthesis of pyrrolizidine and indolizidine alkaloids.

    Science.gov (United States)

    Brandi, Alberto; Cardona, Francesca; Cicchi, Stefano; Cordero, Franca M; Goti, Andrea

    2009-08-10

    The synthesis of polyhydroxylated indolizidines and pyrrolizidines belonging to the class of iminosugars, endowed with a vast and assorted biological activity, can be achieved in a straightforward manner by a general strategy consisting of a highly stereoselective 1,3-dipolar cycloaddition of polyhydroxylated pyrroline-N-oxides followed by simple transformations of the isoxazolidine adducts. The strategy allows the complete control of the relative and absolute stereochemistry of the numerous stereogenic centers decorating these compounds.

  13. Regioselective One-Pot Synthesis of Triptycenes via Triple-Cycloadditions of Arynes to Ynolates.

    Science.gov (United States)

    Umezu, Satoshi; Dos Passos Gomes, Gabriel; Yoshinaga, Tatsuro; Sakae, Mikei; Matsumoto, Kenji; Iwata, Takayuki; Alabugin, Igor; Shindo, Mitsuru

    2017-01-24

    We developed the novel one-pot synthetic method of substituted triptycenes by the reaction of ynolates and arynes. This four-step process involves three cycloadditions and electrocyclic ring opening of the strained Dewar anthracene. Each of the three related but structurally distinct classes of nucleophiles (ynolate, enolate, and anthracenolate) reacts with o-benzyne in the same predictable manner controlled by chelation and negative hyperconjugation. The resulting functionalized C3 -symmetrical triptycenes hold promise in the design of functional materials.

  14. 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.

  15. 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

  16. 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)

  17. Soluble Polymer-Supported Synthesis of Pyrazoles via 1,3-Dipolar Cycloaddition Strategy

    Institute of Scientific and Technical Information of China (English)

    LIN,Xu-Feng(林旭锋); WANG,Yan-Guang(王彦广); DING,Han-Feng(丁寒锋)

    2004-01-01

    Rapid parallel liquid-phase synthesis of pyrazoles has first been developed.The 1,3-dipolar cycloaddition between nitrilimines generated in situ and soluble polymer-supported alkynyl or alkenyl dipolarophiles in parallel one-pot fashion gave the corresponding PEG-supported regioisomeric pyrazoles or regiospecific pyrazolines.The latter was assuredly oxidated by DDQ to PEG-supported regiospecific pyrazoles.Cleavage from the support under mild conditions afforded pyrazoles in good yields and high purity.

  18. 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.

  19. A 11-Steps Total Synthesis of Magellanine through a Gold(I)-Catalyzed Dehydro Diels-Alder Reaction.

    Science.gov (United States)

    McGee, Philippe; Bétournay, Geneviève; Barabé, Francis; Barriault, Louis

    2017-01-12

    We have developed an innovative strategy for the formation of angular carbocycles via a gold(I)-catalyzed dehydro Diels-Alder reaction. This transformation provides rapid access to a variety of complex angular cores in excellent diastereoselectivities and high yields. The usefulness of this Au(I) -catalyzed cycloaddition was further demonstrated by accomplishing a 11-steps total synthesis of (±)-magellanine.

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

    Directory of Open Access Journals (Sweden)

    Andreas Gansäuer

    2014-07-01

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

  1. Synthesis of Novel Fuctionalized Glycosides Based on 1,3-Dipolar Cycloaddition

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    1 Results 1,3-Dipolar cycloaddition reaction is one of the most common methods for preparing various five membered heterocycles,and provides a conveniet protocols for constructing C-C bond with functional groups.The reaction has also been successfully used in the syntheses of C-glycosides and other sacharride derivatives.We wish to present herein our recent approaches on the synthesis of novel C-amino-glycosides,C-aminodisaccharides,spiro heterocyclic glycosides and heterocycle linked C-disaccharides,et...

  2. 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.

  3. Theoretical Study of 1,3-Dipolar Cycloaddition of Hydrazoic Acid to Substituted Ynamines

    Institute of Scientific and Technical Information of China (English)

    Xiaofang Chen; Kun Yang; Keli Han

    2009-01-01

    The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers,4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory. The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.

  4. Theoretical Study of 1,3-Dipolar Cycloaddition of Hydrazoic Acid to Substituted Ynamines

    Science.gov (United States)

    Chen, Xiao-fang; Yang, Kun; Han, Ke-li

    2009-04-01

    The 1,3-dipolar cycloaddition reactions of various substituted ynamines with hydrazoic acid were theoretically investigated with the high-accuracy CBS-QB3 method. Two regioisomers, 4-amine, and 5-amine substituted adducts, were obtained, with the former as the preferred yield. This regioselectivity is rationalized by the frontier molecular orbital theory. The reactivity and synchronicity are enhanced with the increase of the electron-withdrawing character of the substitute on ynamine fragment. The calculations also show that the effect of solvent increases the activation energy, and the reaction becomes even harder in polar solvent.

  5. 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.

  6. 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.

  7. 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.

  8. Metal- and Protection-Free [4 + 2] Cycloadditions of Alkynes with Azadienes: Assembly of Functionalized Quinolines.

    Science.gov (United States)

    Saunthwal, Rakesh K; Patel, Monika; Verma, Akhilesh K

    2016-05-06

    A base promoted, protection-free, and regioselective synthesis of highly functionalized quinolines via [4 + 2] cycloaddition of azadienes (generated in situ from o-aminobenzyl alcohol) with internal alkynes has been discovered. The reaction tolerates a wide variety of functional groups which has been successfully extended with diynes, (2-aminopyridin-3-yl)methanol, and 1,4-bis(phenylethynyl)benzene to afford (Z)-phenyl-2-styrylquinolines, phenylnaphthyridine, and alkyne-substituted quinolines, respectively. The proposed mechanism and significant role of the solvent were well supported by isolating the azadiene intermediate and deuterium-labeling studies.

  9. 1-Azadienes in cycloaddition and multicomponent reactions towards N-heterocycles.

    Science.gov (United States)

    Groenendaal, Bas; Ruijter, Eelco; Orru, Romano V A

    2008-11-21

    1-Azadienes are versatile building blocks for the efficient construction of various N-heterocycles. Depending on the substitution pattern and reaction partner, they may participate in a range of different reactions. An overview of recent methods for the generation of 1-azadienes is presented, as well as their application in cycloaddition, electrocyclization, and multicomponent reactions. Considering the broad range of reactivities and resulting heterocyclic scaffold structures, 1-azadienes are very useful reactive intermediates for the development of modular reaction sequences in diversity-oriented synthesis.

  10. Enantioselective Cycloaddition Reactions Catalyzed by BINOL-Derived Phosphoric Acids and N-Triflyl Phosphoramides: Recent Advances.

    Science.gov (United States)

    Held, Felix E; Grau, Dominik; Tsogoeva, Svetlana B

    2015-09-03

    Over the last several years there has been a huge increase in the development and applications of new efficient organocatalysts for enantioselective pericyclic reactions, which represent one of the most powerful types of organic transformations. Among these processes are cycloaddition reactions (e.g., [3+2]; formal [3+3]; [4+2]; vinylogous [4+2] and 1,3-dipolar cycloadditions), which belong to the most utilized reactions in organic synthesis of complex nitrogen- and oxygen-containing heterocyclic molecules. This review presents the breakthrough realized in this field using chiral BINOL-derived phosphoric acids and N-triflyl phosphoramide organocatalysts.

  11. Stereocontrol of the Schiff Base of Substituted Benzaldehyde to Staudinger Cycloaddition Reaction

    Institute of Scientific and Technical Information of China (English)

    齐传民; 杨凌春; 孙彭利

    2003-01-01

    Syntheses of 4 novel chiral azetidin-2-one derivatives,which were characterized by 1H NMR,IR,specific rotation and elemental analysis,through Staudinger cycloaddition reaction of Schiff base of benzaldehyde with chlorine substitution at different position in benzene ring,were described.For the first time,this type of 3S,4R configuration azetidin-2-one monocrystals with many chiral centers [(3S,4R)-3-hydroxy-N-[(S)-(1-phenyl)ethyl]-4-(2''-chlorophenyl)-azetidin-2-one monocrystal]were obtained,the structures of which were determined by X-ray diffraction analysis.The effects of Schiff base of benzaldehyde with chlorine substitution at different position in benzene ring on stereoselectivity of Staudinger cycloaddition reaction products were discussed and the results are showed as below:2-chlorophenyl Schiff base favored to yield 3S,4R configuration product,but 4-chlorophenyl Schiff base favored to yield 3R,4S configuration product.The reaction orientation of 2,4-dichlorophenyl Schiff base was determined by corporate effect of 2- and 4-chlorine,and that of the 4-chlorine was more obvious.In contrast to 4-chlorophenyl,although the main product was 3R,4S configuration,3-chlorophenyl owned lower selectivity.

  12. Cytotoxic conjugates of betulinic acid and substituted triazoles prepared by Huisgen Cycloaddition from 30-azidoderivatives

    Science.gov (United States)

    Sidova, Veronika; Zoufaly, Pavel; Pokorny, Jan; Dzubak, Petr; Hajduch, Marian; Popa, Igor

    2017-01-01

    In this work, we describe synthesis of conjugates of betulinic acid with substituted triazoles prepared via Huisgen 1,3-cycloaddition. All compounds contain free 28-COOH group. Allylic bromination of protected betulinic acid by NBS gave corresponding 30-bromoderivatives, their substitution with sodium azides produced 30-azidoderivatives and these azides were subjected to CuI catalysed Huisgen 1,3-cycloaddition to give the final conjugates. Reactions had moderate to high yields. All new compounds were tested for their in vitro cytotoxic activities on eight cancer and two non-cancer cell lines. The most active compounds were conjugates of 3β-O-acetylbetulinic acid and among them, conjugate with triazole substituted by benzaldehyde 9b was the best with IC50 of 3.3 μM and therapeutic index of 9.1. Five compounds in this study had IC50 below 10 μM and inhibited DNA and RNA synthesis and caused block in G0/G1 cell cycle phase which is highly similar to actinomycin D. It is unusual that here prepared 3β-O-acetates were more active than compounds with the free 3-OH group and this suggests that this set may have common mechanism of action that is different from the mechanism of action of previously known 3β-O-acetoxybetulinic acid derivatives. Benzaldehyde type conjugate 9b is the best candidate for further drug development. PMID:28158265

  13. Light-induced hetero-Diels-Alder cycloaddition: a facile and selective photoclick reaction.

    Science.gov (United States)

    Arumugam, Selvanathan; Popik, Vladimir V

    2011-04-13

    2-Napthoquinone-3-methides (oNQMs) generated by efficient photodehydration (Φ=0.2) of 3-(hydroxymethyl)-2-naphthol undergo facile hetero-Diels-Alder addition (k(D-A)∼ 4×10(4) M(-1) s(-1)) to electron-rich polarized olefins in an aqueous solution. The resulting photostable benzo[g]chromans are produced in high to quantitative yield. The unreacted oNQM is rapidly hydrated (k(H2O) ∼145 s(-1)) to regenerate the starting diol. This competition between hydration and cycloaddition makes oNQMs highly selective, since only vinyl ethers and enamines are reactive enough to form the Diels-Alder adduct in an aqueous solution; no cycloaddition was observed with other types of alkenes. To achieve photolabeling or photoligation of two substrates, one is derivatized with a vinyl ether moiety, while 3-(hydroxymethyl)-2-naphthol is attached to the other via an appropriate linker. The light-induced Diels-Alder "click" strategy permits the formation of either a permanent or hydrolytically labile linkage. Rapid kinetics of this photoclick reaction (k=4×10(4) M(-1) s(-1)) is useful for time-resolved applications. The short lifetime (τ ∼7 ms in H(2)O) of the active form of the photoclick reagent prevents its migration from the site of irradiation, thus, allowing for spatial control of the ligation or labeling.

  14. Opioid receptor probes derived from cycloaddition of the hallucinogen natural product salvinorin A.

    Science.gov (United States)

    Lozama, Anthony; Cunningham, Christopher W; Caspers, Michael J; Douglas, Justin T; Dersch, Christina M; Rothman, Richard B; Prisinzano, Thomas E

    2011-04-25

    As part of our continuing efforts toward more fully understanding the structure-activity relationships of the neoclerodane diterpene salvinorin A, we report the synthesis and biological characterization of unique cycloadducts through [4+2] Diels-Alder cycloaddition. Microwave-assisted methods were developed and successfully employed, aiding in functionalizing the chemically sensitive salvinorin A scaffold. This demonstrates the first reported results for both cycloaddition of the furan ring and functionalization via microwave-assisted methodology of the salvinorin A skeleton. The cycloadducts yielded herein introduce electron-withdrawing substituents and bulky aromatic groups into the C-12 position. Kappa opioid (KOP) receptor space was explored through aromatization of the bent oxanorbornadiene system possessed by the cycloadducts to a planar phenyl ring system. Although dimethyl- and diethylcarboxylate analogues 5 and 6 retain some affinity and selectivity for KOP receptors and are full agonists, their aromatized counterparts 13 and 14 have reduced affinity for KOP receptors. The methods developed herein signify a novel approach toward rapidly probing the structure-activity relationships of furan-containing natural products.

  15. 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.

  16. 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.

  17. 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

    2015-01-02

    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.

  18. Asymmetric 1,3-dipolar cycloaddition of nitrile oxides to chiral acryloyl esters bearing glucofuranose as auxiliary

    Institute of Scientific and Technical Information of China (English)

    ZHANG, Ao; KAN, Ying; JIANG, Biao

    2000-01-01

    Asymmetric 1,3-dipolar cycloaddition of nitrile oxides to an acryloyl ester (1) derived from 1,2: 5,6-di- O-isopropylidene glucose (6) was studied. Solvent and temperature effect was discussed. The single diastereoisomer was isolated with high diastereoselective excess.

  19. 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.

  20. Stereoselective cyclo-addition reactions of azomethine ylides catalysed by in situ generated Ag(I/bisphosphine complexes

    Directory of Open Access Journals (Sweden)

    VLADIMIR SAVIĆ

    2010-01-01

    Full Text Available Stereoselective cyclo-addition reactions of azomethine ylides promoted by in situ generated Ag(I/bisphosphine complexes were studied. Under the optimised conditions, the pyrrolidine products were isolated in up to 84 % yield and with up to 71 % e.e. The effects of various reaction variables on the stereoselectivity were also investigated.

  1. 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.

  2. 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

  3. 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…

  4. 1,3-Dipolar Cycloaddition of Nitrones with Electron-richAlkenes Catalyzed by Yb(OTf)3

    Institute of Scientific and Technical Information of China (English)

    QIAN, Chang-Tao; WANG, Long-Cheng; CHEN, Rui-Fang

    2001-01-01

    1,3-Dipolar cycloaddition of nitrones with ethyl vinyl ether or 2, 3-dihydrofuran proceeds smoothly in the presence of a catalytic amount (10 mol% ) of ytterbium triflate to afford isoxazolidines and dicyclic isoxazolidine respectively with good yields ahd high stereoselectivity.

  5. 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 ...

  6. 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.

  7. 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.

  8. 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 distribution. Hot stage optical polarizing microscopic investigation confirms the liquid crystalline nature of the polymers with lengthy flexible spacers, while the short chain containing polymers does not show the mesomorphic properties. Differential scanning calorimetric analysis confirms the formation of mesophase in some of the polymers, and it is in accordance with the microscopic results. Thermal stabilities of the polymers were analyzed by thermogravimetric analysis.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  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. 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.

  17. Hybrid NS ligands supported Cu(I)/(II) complexes for azide-alkyne cycloaddition reactions.

    Science.gov (United States)

    Bai, Shi-Qiang; Jiang, Lu; Zuo, Jing-Lin; Hor, T S Andy

    2013-08-21

    Three copper complexes of nitrogen-sulfur donor ligands, [CuBr₂(L1)] (1), [CuCl₂(L2)₂] (2) and [Cu₂I₂(L3)]n (3) (L1 = bis(2-cyclohexylsulfanylethyl)amine, L2 = 2-(benzylsulfanylmethyl)pyridine and L3 = 2-(4-pyridylsulfanylmethyl)pyridine), have been synthesized and characterized by single-crystal X-ray diffraction (XRD), powder XRD and TGA analysis. Complexes 1 and 2 are mononuclear Cu(II) complexes and are EPR active with distorted square-pyramidal and octahedral geometry, respectively. Complex 3 is a two-dimensional tetrahedral Cu(I) coordination polymer with 16- and 20-membered metallocycles. These complexes show good catalytic activities for one-pot azide-alkyne cycloaddition reactions in CH₃OH-H₂O.

  18. 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

  19. 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.

  20. 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.

  1. Recent Advances in Recoverable Systems for the Copper-Catalyzed Azide-Alkyne Cycloaddition Reaction (CuAAC

    Directory of Open Access Journals (Sweden)

    Alessandro Mandoli

    2016-09-01

    Full Text Available The explosively-growing applications of the Cu-catalyzed Huisgen 1,3-dipolar cycloaddition reaction between organic azides and alkynes (CuAAC have stimulated an impressive number of reports, in the last years, focusing on recoverable variants of the homogeneous or quasi-homogeneous catalysts. Recent advances in the field are reviewed, with particular emphasis on systems immobilized onto polymeric organic or inorganic supports.

  2. [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.

  3. 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.

  4. Enantioselective formal [3+3] cycloadditions of ketones and cyclic 1-azadienes by cascade enamine-enamine catalysis.

    Science.gov (United States)

    He, Xiao-Long; Xiao, You-Cai; Du, Wei; Chen, Ying-Chun

    2015-02-16

    An asymmetric formal [3+3] cycloaddition process with diversely structured aliphatic ketones and electron-deficient cyclic 1-azadienes was developed by cascade enamine-enamine catalysis of a cinchona-based primary amine. This sequence involved a domino Michael addition-Mannich reaction to afford spirocyclic architectures in excellent diastereo- and enantioselectivity. Importantly, high regioselectivity was realized for a number of unsymmetrical aliphatic ketone substrates.

  5. Structural Determinants of Alkyne Reactivity in Copper-Catalyzed Azide-Alkyne Cycloadditions

    Directory of Open Access Journals (Sweden)

    Xiaoguang Zhang

    2016-12-01

    Full Text Available This work represents our initial effort in identifying azide/alkyne pairs for optimal reactivity in copper-catalyzed azide-alkyne cycloaddition (CuAAC reactions. In previous works, we have identified chelating azides, in particular 2-picolyl azide, as “privileged” azide substrates with high CuAAC reactivity. In the current work, two types of alkynes are shown to undergo rapid CuAAC reactions under both copper(II- (via an induction period and copper(I-catalyzed conditions. The first type of the alkynes bears relatively acidic ethynyl C-H bonds, while the second type contains an N-(triazolylmethylpropargylic moiety that produces a self-accelerating effect. The rankings of reactivity under both copper(II- and copper(I-catalyzed conditions are provided. The observations on how other reaction parameters such as accelerating ligand, reducing agent, or identity of azide alter the relative reactivity of alkynes are described and, to the best of our ability, explained.

  6. The cobalt-mediated [2+2+2]cycloaddition of thiophenes and benzofurans to alkynes

    Energy Technology Data Exchange (ETDEWEB)

    Malaska, M.J.

    1991-01-01

    The cobalt-mediated [2+2+2]cycloaddition of thiophenes and benzofurans to alkynes was investigated. The cocyclization of 2-propynyloxymethylthiophenes provided two types of cyclohexadiene complexes. It was found that one of these complexes could be converted to the other by a thermal rearrangement. This novel transformation was investigated by deuterium-labelling and kinetic studies, and a mechanism was proposed. The complexes could be oxidatively demetallated to provide the liberated organic framework. Further reorganization of these dienes were observed during the decomplexation process and in the presence of CpCo(C[sub 2]H[sub 4])[sub 2]. In this manner several new heterocyclic ring systems could be constructed from 2-substituted thiophenes. Following the success of the thiophene cyclizations, the cocyclization of the benzofuran nucleus was examined. Reagents and conditions were developed that provide an efficient synthesis of alkynols from carboxylic acids; other functional group interconversions of the alkynols were briefly studied. The synthesis and cyclization of 1-[7-methoxy-4-benzofuranyl]-3-butyn-2-ol produced a cobalt complex containing the A,B,C, and D rings of the morphine skeleton. A synthetic advantage of this methodology would be the ease of substitution at pharmaco-logically relevant C-6 and C-7 positions of the morphine framework. Synthetic routes using a cobalt cyclization strategy were proposed.

  7. Functionalisation of lanthanide complexes via microwave-enhanced Cu(I)-catalysed azide-alkyne cycloaddition.

    Science.gov (United States)

    Szíjjártó, Csongor; Pershagen, Elias; Borbas, K Eszter

    2012-07-07

    Cu(I)-catalysed azide-alkyne cycloaddition reactions were used to functionalise lanthanide(III)-complexes (Ln; La, Eu and Tb) incorporating alkyne or azide reactive groups. Microwave irradiation significantly accelerated the reactions, enabling full conversion to the triazole products in some cases in 5 min. Alkyl and aryl azides and alkyl and aryl alkynes could all serve as coupling partners. These reaction conditions proved efficient for cyclen-tricarboxylates and previously unreactive cyclen-tris-primary amide chelates. The synthesis of heterobimetallic (Eu/Tb, EuTb17 and Eu/La, EuLa17) and heterotrimetallic (Eu/La/Eu) complexes was achieved in up to 60% isolated yield starting from coumarin 2-appended alkynyl complexes Tb16 or La16 and an azido-Eu complex Eu4, and bis-alkynyl La-complex La5 and Eu4, respectively. EuTb17 displayed dual Eu(III) and Tb(III)-emission upon antenna-centred excitation.

  8. Concise Total Synthesis of Lundurines A-C Enabled by Gold Catalysis and a Homodienyl Retro-Ene/Ene Isomerization.

    Science.gov (United States)

    Kirillova, Mariia S; Muratore, Michael E; Dorel, Ruth; Echavarren, Antonio M

    2016-03-23

    The total synthesis of lundurines A-C has been accomplished in racemic and enantiopure forms in 11-13 and 12-14 steps, respectively, without protection/deprotection of functional groups, by a novel tandem double condensation/Claisen rearrangement, a gold(I)-catalyzed alkyne hydroarylation, a cyclopropanation via formal [3 + 2] cycloaddition/nitrogen extrusion, and a remarkable olefin migration through a vinylcyclopropane retro-ene/ene reaction that streamlines the endgame.

  9. Concise Total Synthesis of Lundurines A–C Enabled by Gold Catalysis and a Homodienyl Retro-Ene/Ene Isomerization

    Science.gov (United States)

    2016-01-01

    The total synthesis of lundurines A–C has been accomplished in racemic and enantiopure forms in 11–13 and 12–14 steps, respectively, without protection/deprotection of functional groups, by a novel tandem double condensation/Claisen rearrangement, a gold(I)-catalyzed alkyne hydroarylation, a cyclopropanation via formal [3 + 2] cycloaddition/nitrogen extrusion, and a remarkable olefin migration through a vinylcyclopropane retro-ene/ene reaction that streamlines the endgame. PMID:26963149

  10. 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.

  11. Copper-catalyzed Huisgen 1,3-dipolar cycloaddition under oxidative conditions: polymer-assisted assembly of 4-acyl-1-substituted-1,2,3-triazoles.

    Science.gov (United States)

    Diz, Paula M; Coelho, Alberto; El Maatougui, Abdelaziz; Azuaje, Jhonny; Caamaño, Olga; Gil, Álvaro; Sotelo, Eddy

    2013-07-05

    We herein document the first example of a reliable copper-catalyzed Huisgen 1,3-dipolar cycloaddition under oxidative conditions. The combined use of two polymer-supported reagents (polystyrene-1,5,7-triazabicyclo[4,4,0]dec-5-ene/Cu and polystyrene-2-iodoxybenzamide) overcomes the thermodynamic instability of copper(I) species toward oxidation, enabling the reliable Cu-catalyzed Huisgen 1,3-dipolar cycloadditions in the presence of an oxidant agent. This polymer-assisted pathway, not feasible under conventional homogeneous conditions, provides a direct assembly of 4-acyl-1-substituted-1,2,3-triazoles, contributing to expand the reliability and scope of Cu(I)-catalyzed alkyne-azide cycloaddition.

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

    Science.gov (United States)

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

    2009-02-06

    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

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Synthesis of indazoles by the [3+2] cycloaddition of diazo compounds with arynes and subsequent acyl migration.

    Science.gov (United States)

    Liu, Zhijian; Shi, Feng; Martinez, Pablo D G; Raminelli, Cristiano; Larock, Richard C

    2008-01-04

    The [3+2] cycloaddition of a variety of diazo compounds with o-(trimethylsilyl)aryl triflates in the presence of CsF or TBAF at room temperature provides a very direct, efficient approach to a wide range of potentially biologically and pharmaceutically interesting substituted indazoles in good to excellent yields under mild reaction conditions. Simple diazomethane derivatives afford N-unsubstituted indazoles or 1-arylated indazoles, depending upon the stoichiometry of the reagents and the reaction conditions, while dicarbonyl-containing diazo compounds undergo carbonyl migration to afford 1-acyl or 1-alkoxycarbonyl indazoles selectively.

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

    KAUST Repository

    Alkordi, Mohamed Helmi

    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.

  20. 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.

  1. Efficient microwave assisted synthesis of novel 1,2,3-triazole-sucrose derivatives by cycloaddition reaction of sucrose azides and terminal alkynes.

    Science.gov (United States)

    Potewar, Taterao M; Petrova, Krasimira T; Barros, M Teresa

    2013-09-20

    Novel 1-(1',2,3,3',4,4',6-hepta-O-acetyl-6'-deoxy-sucros-6'-yl)-4-substituted-1,2,3-triazoles were synthesized by microwave assisted copper catalyzed 1,3-dipolar cycloaddition of sucrose derived azides with terminal alkynes in excellent yields and in short reaction times. The compound 1',2,3,3',4,4',6-hepta-O-acetyl-6'-azido-6'-deoxy-sucrose was regioselectively synthesized from sucrose by improved procedure and used for the cycloadditions. By combining carbohydrate and 1,2,3-triazole structural motifs, a library of 1,2,3-triazole-sucrose conjugates have been obtained.

  2. 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.

  3. A Cycloaddition Strategy for Use toward Berkelic Acid, an MMP Inhibitor and Potent Anticancer Agent Displaying a Unique Chroman Spiroketal Motif.

    Science.gov (United States)

    Huang, Yaodong; Pettus, Thomas R R

    2008-05-11

    A kinetically controlled diastereoselective cycloaddition between a chiral enol ether and an ortho-quinone methide (o-QM) produces a chroman spiroketal motif that is found in the core of berkelic acid, a novel matrix metalloproteinase (MMP) inhibitor and potent anticancer agent. The transformation lays the groundwork for preparation of future inhibitors aimed at distinguishing among the active sites of the twenty-three known MMP. Experimental findings suggest that the stereochemistry that emerges from cycloaddition is opposite that which results from thermodynamic ketalization.

  4. 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.

  5. 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.

  6. Cobalt-Catalyzed [2π + 2π] Cycloadditions of Alkenes: Scope, Mechanism, and Elucidation of Electronic Structure of Catalytic Intermediates.

    Science.gov (United States)

    Schmidt, Valerie A; Hoyt, Jordan M; Margulieux, Grant W; Chirik, Paul J

    2015-06-24

    Aryl-substituted bis(imino)pyridine cobalt dinitrogen compounds, ((R)PDI)CoN2, are effective precatalysts for the intramolecular [2π + 2π] cycloaddition of α,ω-dienes to yield the corresponding bicyclo[3.2.0]heptane derivatives. The reactions proceed under mild thermal conditions with unactivated alkenes, tolerating both amine and ether functional groups. The overall second order rate law for the reaction, first order with respect to both the cobalt precatalyst and the substrate, in combination with electron paramagnetic resonance (EPR) spectroscopic studies established the catalyst resting state as dependent on the identity of the precatalyst and diene substrate. Planar S = ½ κ(3)-bis(imino)pyridine cobalt alkene and tetrahedral κ(2)-bis(imino)pyridine cobalt diene complexes were observed by EPR spectroscopy and in the latter case structurally characterized. The hemilabile chelate facilitates conversion of a principally ligand-based singly occupied molecular orbital (SOMO) in the cobalt dinitrogen and alkene compounds to a metal-based SOMO in the diene intermediates, promoting C-C bond-forming oxidative cyclization. Structure-activity relationships on bis(imino)pyridine substitution were also established with 2,4,6-tricyclopentyl-substituted aryl groups, resulting in optimized catalytic [2π + 2π] cycloaddition. The cyclopentyl groups provide a sufficiently open metal coordination sphere that encourages substrate coordination while remaining large enough to promote a challenging, turnover-limiting C(sp(3))-C(sp(3)) reductive elimination.

  7. 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.

  8. 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

  9. 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 compatibility...

  10. Mono and dinuclear arene ruthenium(II) triazoles by 1,3-dipolar cycloadditions to a coordinated azide in ruthenium(II) compounds

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Svitlyk, V.; Mozharivskyj, Y.

    The dimeric Eta sup(6)-hexamethylbenzene ruthenium(II) triazole compounds of formulation (((Eta sup(6)-C sub(6)Me Sub(6))Ru(N sub(3)C sub(2)(CO sub(2)R)sub(2)) sub(2) - (mu C sub(2)O sub(4))) have been synthesized by 1,3-diploar cycloadditions...

  11. 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,

  12. A highly active and reusable copper(I)-tren catalyst for the "click" 1,3-dipolar cycloaddition of azides and alkynes.

    Science.gov (United States)

    Candelon, Nicolas; Lastécouères, Dominique; Diallo, Abdou Khadri; Aranzaes, Jaime Ruiz; Astruc, Didier; Vincent, Jean-Marc

    2008-02-14

    The copper(I) complex [Cu(C18(6)tren)]Br 1 (C18(6)tren = tris(2-dioctadecylaminoethyl)amine) which exhibits a good stability towards aerobic conditions is a versatile, highly reactive and recyclable catalyst for the Huisgen cycloaddition of azides with terminal or internal alkynes and is a useful catalyst for the preparation of "click" dendrimers.

  13. 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.

  14. 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.

  15. New synthesis of 1-substituted-1H-indazoles via 1,3-dipolar cycloaddition of in situ generated nitrile imines and benzyne.

    Science.gov (United States)

    Spiteri, Christian; Keeling, Steve; Moses, John E

    2010-08-06

    A new synthesis of 1-substituted-1H-indazoles via 1,3-dipolar cycloaddition of nitrile imines to benzyne is described. The reaction is completed within 5 min, affording the corresponding N(1)-C(3) disubstituted indazoles in moderate to excellent yields.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Ligand-enabled multiple absolute stereocontrol in metal-catalysed cycloaddition for construction of contiguous all-carbon quaternary stereocentres.

    Science.gov (United States)

    Ohmatsu, Kohsuke; Imagawa, Naomichi; Ooi, Takashi

    2014-01-01

    The development of a general catalytic method for the direct and stereoselective construction of contiguous all-carbon quaternary stereocentres remains a formidable challenge in chemical synthesis. Here, we report a highly enantio- and diastereoselective [3+2] annulation reaction of 5-vinyloxazolidinones and activated trisubstituted alkenes catalysed by a palladium complex bearing a newly devised phosphine ligand with a chiral ammonium salt component, which enables the single-step construction of three contiguous stereocentres, including vicinal all-carbon quaternary stereocentres, in a five-membered heterocyclic framework. This stereoselective cycloaddition protocol relies on the remarkable ability of the chiral ligand to rigorously control the absolute stereochemistry of each chiral centre associated with the multiple bond-forming events, and provides a reliable catalytic process for the asymmetric synthesis of densely functionalized pyrrolidines.

  2. A Straightforward Route to Enantiopure Pyrrolizidines and Indolizidines by Cycloaddition to Pyrroline N-Oxides Derived from the Chiral Pool

    Directory of Open Access Journals (Sweden)

    Alberto Brandi

    1998-12-01

    Full Text Available Enantiomerically pure, five membered cyclic nitrones, easily obtained in large amounts from protected hydroxyacids and aminoacids such as D- and L-tartaric, L-malic, and L-aspartic acids, give cycloaddition reactions with a good diastereocontrol. The adducts of L-malic and L-aspartic acids derived from addition of nitrones to dimethyl maleate and g-crotonolactone were easily converted into enantiopure pyrrolizidinones, which can be transformed into polyhydroxypyrrolidines or polyhydroxypyrrolizidines, both interesting compounds as potential glycosidase inhibitors. The method is suitable for natural products synthesis as exemplified by a straightforward and convenient access to the pyrrolizidine alkaloid necine base (–-hastanecine, as well as to indolizidine alkaloids, i.e. (+- lentiginosine.

  3. 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.

  4. Regioselective Synthesis of C-3-Functionalized Quinolines via Hetero-Diels-Alder Cycloaddition of Azadienes with Terminal Alkynes.

    Science.gov (United States)

    Saunthwal, Rakesh K; Patel, Monika; Verma, Akhilesh K

    2016-08-05

    A highly efficient metal and protection-free approach for the regioselective synthesis of C-3-functionalized quinolines from azadienes (in situ generated from 2-aminobenzyl alcohol) and terminal alkynes through [4 + 2] cycloaddition has been developed. An unprecedented reaction of 2-aminobenzyl alcohol with 1,3- and 1,4-diethynylbenzene provided the C-3 tolylquinolines via [4 + 2] HDA and oxidative decarboxylation. The -NH2 group directed mechanistic approach was well supported by the control experiments and deuterium-labeling studies and by isolating the azadiene intermediate. The reactivity and selectivity of unprotected azadiene in metal-free base-assisted hetero-Diels-Alder reaction is exploited to quickly assemble an important class of C-3-functionalized quinolines, which are difficult to access.

  5. 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.

  6. 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.

  7. Imino [4+4] cycloaddition products as exclusive and biologically relevant acrolein-amine conjugates are intermediates of 3-formyl-3,4-dehydropiperidine (FDP), an acrolein biomarker.

    Science.gov (United States)

    Takamatsu, Masayuki; Fukase, Koichi; Kurbangalieva, Almira; Tanaka, Katsunori

    2014-11-15

    We demonstrated synthetically that the eight-membered heterocycles 2,6,9-triazabicyclo[3.3.1]nonanes and 1,5-diazacyclooctanes are the initial and exclusive products of the reaction, through an imino [4+4] cycloaddition, of biologically relevant amines with acrolein. The stabilities of the aminoacetals within the eight-membered heterocycles determined whether the product was subsequently transformed gradually into the 3-formyl-3,4-dehydropiperidine (FDP), which is widely used as an oxidative stress marker. The reactivity profiles discovered in this study suggested that some of the imino [4+4] cycloaddition products are reactive intermediates of FDP and contribute to the mechanisms underlying the oxidative stress response to acrolein.

  8. 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.

  9. 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.

  10. Zn-catalyzed enantio- and diastereoselective formal [4 + 2] cycloaddition involving two electron-deficient partners: asymmetric synthesis of piperidines from 1-azadienes and nitro-alkenes.

    Science.gov (United States)

    Chu, John C K; Dalton, Derek M; Rovis, Tomislav

    2015-04-08

    We report a catalytic asymmetric synthesis of piperidines through [4 + 2] cycloaddition of 1-azadienes and nitro-alkenes. The reaction uses earth abundant Zn as catalyst and is highly diastereo- and regioselective. A novel BOPA ligand (F-BOPA) confers high reactivity and enantioselectivity in the process. The presence of ortho substitution on the arenes adjacent to the bis(oxazolines) was found to be particularly impactful, due to limiting the undesired coordination of 1-azadiene to the Lewis acid and thus allowing the reaction to be carried out at lower temperature. A series of secondary kinetic isotope effect studies using a range of ligands implicates a stepwise mechanism for the transformation, involving an initial Michael-type addition of the imine to the nitro-alkene followed by a cyclization event. The stepwise mechanism obviates the electronic requirement inherent to a concerted mechanism, explaining the successful cycloaddition between two electron-deficient partners.

  11. Rh(II) Catalyzed High Order Cycloadditions of 8-Azaheptafulvenes with N-Sulfonyl 1,2,3-Triazloes or α-Oxo Diazocompounds.

    Science.gov (United States)

    Chen, Wei; Bai, Ya-Li; Luo, Yong-Chun; Xu, Peng-Fei

    2017-01-20

    A novel strategy was developed for the application of Rh carbenes generated from readily accessible N-sulfonyl 1,2,3,-triazoles or diazocompouds in the high order cycloadditions, which offered an efficient route to a variety of N-containing medium-sized rings. The process provided a wide range of cyclohepta[b]pyrazine and cyclohepta[b]pyrrolone derivatives with high yields.

  12. Scaffold oriented synthesis. Part 3: design, synthesis and biological evaluation of novel 5-substituted indazoles as potent and selective kinase inhibitors employing [2+3] cycloadditions.

    Science.gov (United States)

    Akritopoulou-Zanze, Irini; Wakefield, Brian D; Gasiecki, Alan; Kalvin, Douglas; Johnson, Eric F; Kovar, Peter; Djuric, Stevan W

    2011-03-01

    We report the synthesis and biological evaluation of 5-substituted indazoles and amino indazoles as kinase inhibitors. The compounds were synthesized in a parallel synthesis fashion from readily available starting materials employing [2+3] cycloaddition reactions and were evaluated against a panel of kinase assays. Potent inhibitors were identified for numerous kinases such as Rock2, Gsk3β, Aurora2 and Jak2.

  13. DMAP-catalyzed [3 + 2] and [4 + 2] cycloaddition reactions between [60]fullerene and unmodified Morita-Baylis-Hillman adducts in the presence of Ac2O.

    Science.gov (United States)

    Yang, Hai-Tao; Ren, Wen-Long; Miao, Chun-Bao; Dong, Chun-Ping; Yang, Yang; Xi, Hai-Tao; Meng, Qi; Jiang, Yan; Sun, Xiao-Qiang

    2013-02-01

    One-step DMAP-catalyzed [3 + 2] and [4 + 2] cycloaddition reactions between C(60) and unmodified Morita-Baylis-Hillman adducts in the presence of Ac(2)O have been developed for the easy preparation of cyclopentene- and cyclohexene-fused [60]fullerene derivatives. When the MBH adducts bear an alkyl group, two different reaction pathways could be controlled selectively depending on the conditions.

  14. 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.

  15. 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.

  16. 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)

  17. 1,3-Dipolar Cycloaddition Reactions of 1-(4-Phenylphenacyl-1,10-phenanthrolinium N-Ylide with Activated Alkynes and Alkenes

    Directory of Open Access Journals (Sweden)

    A. Badoiu

    2005-02-01

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

  18. A Facile Access to Fluorinated Pyrrolidines via Catalytic Asymmetric 1,3-Dipolar Cycloaddition of Azomethine Ylides with Methyl a-Fluoroacrylate

    Institute of Scientific and Technical Information of China (English)

    严定策; 李清华; 王春江

    2012-01-01

    Asymmetric 1,3-dipolar cycloaddition of methyl a-fluoroacrylate with azomethine ylides for the construction of optically active fluorinated pyrrolidines bearing one unique fluorinated quaternary and two tertiary stereogenic cen- ters has been achieved with Cu(CH3CN)4BF4/TF-BiphamPhos complexes for the first time. This catalytic system performs well over a broad scope of substrates, providing the synthetically useful adducts in good yields and excel- lent diastereoselectivities and good to high enantioselectivities.

  19. Development of a tailor-made bis(oxazolidine)pyridine-metal catalyst for the [3+2] cycloaddition of azomethine imines with propiolates.

    Science.gov (United States)

    Arai, Takayoshi; Ogino, Yuta; Sato, Toru

    2013-09-14

    A series of bis(oxazolidine)pyridine ligands (the PyBodines) were newly designed and synthesized for the development of a highly efficient, tailor-made catalyst for the [3+2] cycloaddition of azomethine imines with propiolates. The PyBodine(l-Ala)-Cu(OAc)2 catalyst was selected on the basis of solid-phase catalysis/CD-HTS and exhibited high efficiency, producing the (R)-adducts with excellent enantioselectivity.

  20. Synthesis of Bis-pyrrolizidine-Fused Dispiro-oxindole Analogues of Curcumin via One-Pot Azomethine Ylide Cycloaddition: Experimental and Computational Approach toward Regio- and Diastereoselection.

    Science.gov (United States)

    Bharitkar, Yogesh P; Das, Mohua; Kumari, Neha; Kumari, M Padma; Hazra, Abhijit; Bhayye, Sagar S; Natarajan, Ramalingam; Shah, Siddharth; Chatterjee, Sourav; Mondal, Nirup B

    2015-09-18

    Curcumin has been transformed to racemic curcuminoids via an azomethine ylide cycloaddition reaction using isatin/acenaphthoquinone and proline as the reagents. The products were characterized by extensive 1D/2D NMR analysis and single-crystal X-ray crystallographic studies. The enantiomers of one racemic product were separated by HPLC on a Chiralcel OD-H column and were indeed confirmed by the CD spectra of the separated enantiomers.

  1. Synthesis of ferrocene-labeled steroids via copper-catalyzed azide-alkyne cycloaddition. Reactivity difference between 2β-, 6β- and 16β-azido-androstanes.

    Science.gov (United States)

    Fehér, Klaudia; Balogh, János; Csók, Zsolt; Kégl, Tamás; Kollár, László; Skoda-Földes, Rita

    2012-06-01

    Copper-catalyzed cycloaddition of steroidal azides and ferrocenyl-alkynes were found to be an efficient methodology for the synthesis of ferrocene-labeled steroids. At the same time, a great difference between the reactivity of 2β- or 16β-azido-androstanes and a sterically hindered 6β-azido steroid toward both ferrocenyl-alkynes and simple alkynes, such as phenylacetylene, 1-octyne, propargyl acetate and methyl propiolate, was observed.

  2. Zn-catalyzed Enantio- and Diastereoselective Formal [4+2] Cycloaddition Involving Two Electron-Deficient Partners: Asymmetric Synthesis of Piperidines from 1-Azadienes and Nitroalkenes

    OpenAIRE

    Chu, John C. K.; Dalton, Derek M.; Rovis, Tomislav

    2015-01-01

    We report a catalytic asymmetric synthesis of piperidines through [4+2] cycloaddition of 1-azadienes and nitroalkenes. The reaction uses earth abundant Zn as catalyst, and is highly diastereo- and regio-selective. A novel BOPA ligand (F-BOPA) confers high reactivity and enantioselectivity in the process. The presence of ortho substitution on the arenes adjacent to the bis(oxazolines) was found to be particularly impactful, due to limiting the undesired coordination of 1-azadiene to the Lewis ...

  3. Inverse Electron Demand Diels–Alder Reactions of 1,2,3-Triazines: Pronounced Substituent Effects on Reactivity and Cycloaddition Scope

    Science.gov (United States)

    Anderson, Erin D.; Boger, Dale L.

    2011-01-01

    A systematic study of the inverse electron demand Diels–Alder reactions of 1,2,3-triazines is disclosed, including an examination of the impact of a C5 substituent. Such substituents were found to exhibit a remarkable impact on the cycloaddition reactivity of the 1,2,3-triazine without altering, and perhaps even enhancing, the intrinsic cycloaddition regioselectivity. The study revealed that not only may the reactivity be predictably modulated by a C5 substituent (R = CO2Me > Ph > H), but that the impact is of a magnitude to convert 1,2,3-triazine (1) and its modest cycloaddition scope into a heterocyclic azadiene system with a reaction scope that portends extensive synthetic utility, expanding the range of participating dienophiles. Significantly, the studies define a now powerful additional heterocyclic azadiene, complementary to the isomeric 1,2,4-triazines and 1,3,5-triazines, capable of dependable participation in inverse electron demand Diels–Alder reactions, extending the number of complementary heterocyclic ring systems accessible with implementation of the methodology. PMID:21736324

  4. Rhodium-catalyzed [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes and CO: reaction design, development, application in natural product synthesis, and inspiration for developing new reactions for synthesis of eight-membered carbocycles.

    Science.gov (United States)

    Wang, Yi; Yu, Zhi-Xiang

    2015-08-18

    Practical syntheses of natural products and their analogues with eight-membered carbocyclic skeletons are important for medicinal and biological investigations. However, methods and strategies to construct the eight-membered carbocycles are limited. Therefore, developing new methods to synthesize the eight-membered carbocycles is highly desired. In this Account, we describe our development of three rhodium-catalyzed cycloadditions for the construction of the eight-membered carbocycles, which have great potential in addressing the challenges in the synthesis of medium-sized ring systems. The first reaction described in this Account is our computationally designed rhodium-catalyzed two-component [5 + 2 + 1] cycloaddition of ene-vinylcyclopropanes (ene-VCPs) and CO for the diastereoselective construction of bi- and tricyclic cyclooctenones. The design of this reaction is based on the hypothesis that the C(sp(3))-C(sp(3)) reductive elimination of the eight-membered rhodacycle intermediate generated from the rhodium-catalyzed cyclopropane cleavage and alkene insertion, giving Wender's [5 + 2] cycloadduct, is not easy. Under CO atmosphere, CO insertion may occur rapidly, converting the eight-membered rhodacycle into a nine-membered rhodacycle, which then undergoes an easy C(sp(2))-C(sp(3)) reductive elimination process and furnishes the [5 + 2 + 1] product. This hypothesis was supported by our preliminary DFT studies and also served as inspiration for the development of two [7 + 1] cycloadditions: the [7 + 1] cycloaddition of buta-1,3-dienylcyclopropanes (BDCPs) and CO for the construction of cyclooctadienones, and the benzo/[7 + 1] cycloaddition of cyclopropyl-benzocyclobutenes (CP-BCBs) and CO to synthesize the benzocyclooctenones. The efficiency of these rhodium-catalyzed cycloadditions can be revealed by the application in natural product synthesis. Two eight-membered ring-containing natural products, (±)-asterisca-3(15),6-diene and (+)-asteriscanolide, have been

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

    Science.gov (United States)

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

    2016-01-01

    ‘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. PMID:27703683

  6. 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.

  7. 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.

  8. Chemically directed assembly of photoactive metal oxide nanoparticle heterojunctions via the copper-catalyzed azide-alkyne cycloaddition "click" reaction.

    Science.gov (United States)

    Cardiel, Allison C; Benson, Michelle C; Bishop, Lee M; Louis, Kacie M; Yeager, Joseph C; Tan, Yizheng; Hamers, Robert J

    2012-01-24

    Metal oxides play a key role in many emerging applications in renewable energy, such as dye-sensitized solar cells and photocatalysts. Because the separation of charge can often be facilitated at junctions between different materials, there is great interest in the formation of heterojunctions between metal oxides. Here, we demonstrate use of the copper-catalyzed azide-alkyne cycloaddition reaction, widely referred to as "click" chemistry, to chemically assemble photoactive heterojunctions between metal oxide nanoparticles, using WO(3) and TiO(2) as a model system. X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy verify the nature and selectivity of the chemical linkages, while scanning electron microscopy reveals that the TiO(2) nanoparticles form a high-density, conformal coating on the larger WO(3) nanoparticles. Time-resolved surface photoresponse measurements show that the resulting dyadic structures support photoactivated charge transfer, while measurements of the photocatalytic degradation of methylene blue show that chemical grafting of TiO(2) nanoparticles to WO(3) increases the photocatalytic activity compared with the bare WO(3) film.

  9. 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.

  10. Diradical reaction mechanisms in [3 + 2]-cycloadditions of hetaryl thioketones with alkyl- or trimethylsilyl-substituted diazomethanes.

    Science.gov (United States)

    Mlostoń, Grzegorz; Pipiak, Paulina; Heimgartner, Heinz

    2016-01-01

    Reactions of dihetaryl and aryl/hetaryl thioketones with 2-diazopropane, diazoethane, and (trimethylsilyl)diazomethane were studied at variable temperature. The experiments showed that reactions with 2-diazopropane carried out at -75 °C occur mainly via the initially formed, relatively stable 1,3,4-thiadiazolines as products of the [3 + 2]-cycloaddition of the diazo dipole onto the C=S bond. The latter decompose only at higher temperature (ca. -40 °C) to generate thiocarbonyl S-isopropanide. In the absence of the starting thioketone, the corresponding thiiranes and/or ethene derivatives, formed from them via spontaneous desulfurization, are the main products. In contrast, reactions with diazoethane occurred predominantly via initially formed diradicals, which in cascade processes gave sterically crowded 4,4,5,5-tetrahetaryl-1,3-dithiolanes as major products. Finally, the reaction of dihetaryl thioketones with (trimethylsilyl)diazomethane occur smoothly at -75 °C leading to the corresponding 4,4,5,5-tetrahetaryl-1,3-dithiolanes as the exclusive [3 + 2]-cycloadducts formed via a cascade of postulated diradicals. The presence of S or Se atoms in the hetaryl rings is of importance for stabilizing diradical intermediates. Remarkably, in no single case, the 'head-to-head dimerization' of aryl/hetaryl and dihetaryl substituted thiocarbonyl ylides was observed.

  11. 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.

  12. Properties of Poly(ethylene glycol) Hydrogels Cross-Linked via Strain-Promoted Alkyne-Azide Cycloaddition (SPAAC).

    Science.gov (United States)

    Hodgson, Sabrina M; Bakaic, Emilia; Stewart, S Alison; Hoare, Todd; Adronov, Alex

    2016-03-14

    A series of poly(ethylene glycol) (PEG) hydrogels was synthesized using strain-promoted alkyne-azide cycloaddition (SPAAC) between PEG chains terminated with either aza-dibenzocyclooctynes or azide functionalities. The gelation process was found to occur rapidly upon mixing the two components in aqueous solution without the need for external stimuli or catalysts, making the system a candidate for use as an injectable hydrogel. The mechanical and rheological properties of these hydrogels were found to be tunable by varying the polymer molecular weight and the number of cross-linking groups per chain. The gelation times of these hydrogels ranged from 10 to 60 s at room temperature. The mass-based swelling ratios varied from 45 to 76 at maximum swelling (relative to the dry state), while the weight percent of polymer in these hydrogels ranged from 1.31 to 2.05%, demonstrating the variations in amount of polymer required to maintain the structural integrity of the gel. Each hydrogel degraded at a different rate in PBS at pH = 7.4, with degradation times ranging from 1 to 35 days. By changing the composition of the two starting components, it was found that the Young's modulus of each hydrogel could be varied from 1 to 18 kPa. Hydrogel incubation with bovine serum albumin showed minimal protein adsorption. Finally, a cell cytotoxicity study of the precursor polymers with 3T3 fibroblasts demonstrated that the azide- and strained alkyne-functionalized PEGs are noncytotoxic.

  13. 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.

  14. Theoretical Evaluation of the Global and Local Electrophilicity Patterns to Characterize Hetero Diels-Alder Cycloaddition in the Synthesis of Isoxazolo[4,5-e](1,2,3,4-tetrazine)

    Institute of Scientific and Technical Information of China (English)

    SHARMA,Pratibha; KUMAR,Ashok; SINGH,Jitendra; SAHU,Vinita

    2009-01-01

    A series of substituted dienophiles 1-10 and three 1,2-diazadienes namely D-1, D-2, D-3 were chosen to understand the reactivity and selectivity of Diels-Alder cycloaddition. The global and local electrophilicity patterns have been evaluated on a series of cycloaddition reactions to assess the reaction pathways (NDAC/IEDDAC) using the absolute scale of electrophilicity proposed by Parr et aL Regional electrophilicity at the active sites of the re-agents involved in Diels-Alder processes has been described on a quantitative basis using local or regional electro-philicity index I.e. Fukui function. Good qualitative/quantitative comparison was found between molecular energy gaps and global electronic parameters, which has been employed to assess the cycloaddition pathways successfully.

  15. 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.

  16. Moderating strain without sacrificing reactivity: design of fast and tunable noncatalyzed alkyne-azide cycloadditions via stereoelectronically controlled transition state stabilization.

    Science.gov (United States)

    Gold, Brian; Dudley, Gregory B; Alabugin, Igor V

    2013-01-30

    Recently, we have identified two strategies for selective transition state (TS) stabilization in catalyst-free azide/alkyne cycloadditions. In particular, the transition states for the formation of both 1,4- and 1,5-isomers can be stabilized via hyperconjugative assistance for the C···N bond formation, whereas the 1,5-TS can be stabilized via C-H···X H-bonding interactions. When the hyperconjugative assistance is maximized by the antiperiplanar arrangement of propargylic σ-acceptors relative to the forming bonds, the combination of these TS-stabilizing effects was predicted to lead to ~1 million fold acceleration of the cycloaddition with methyl azide. The present work investigated whether hyperconjugative assistance and H-bonding can be combined with strain activation for the design of even more reactive alkynes and whether reactivity can be turned "on demand." When stereoelectronic amplification is achieved by optimal positioning of σ-acceptors at the endocyclic bonds antiperiplanar to the breaking alkyne π-bonds, the stabilization of the bent alkyne geometry leads to a significant decrease in strain in cyclic alkynes without compromising their reactivity in alkyne-azide cycloadditions. The approach can be used in a modular fashion where the TS stabilizing effects are introduced sequentially until the desired level of reactivity is achieved. A significant increase in reactivity upon the protonation of an endocyclic NH-group suggests a new strategy for the design of click reactions triggered by a pH-change or introduction of an external Lewis acid.

  17. Synthesis of unsymmetrical substituted 1,4-dihydropyridines through thermal and microwave assisted [4+2] cycloadditions of 1-azadienes and allenic esters.

    Science.gov (United States)

    Singh, Lakhwinder; Ishar, M P Singh; Elango, Munusamy; Subramanian, Venkatesan; Gupta, Vivek; Kanwal, Priyanka

    2008-03-21

    Thermal and microwave assisted [4+2] cycloadditions of 1,4-diaryl-1-aza-1,3-butadienes with allenic esters lead to cycloadducts, which after a 1,3-H shift afford variedly substituted unsymmetrical 2-alkyl-1,4-diaryl-3-ethoxycarbonyl-1,4-dihydropyridines in high yields. Reactions carried out under microwave irradiation are cleaner and give higher yields with much shortened reaction times. Density functional theory (DFT) at the B3LYP/6-31G* level has been used to calculate geometric features of the reactants, barrier for s-trans to s-cis and reverse isomerization of azadienes (5a-d, 10a-e), dihedral angles between N(1), C(2), C(3), and C(4) atoms of azadienes along with various indices such as chemical hardness (eta), chemical potential (micro), global electrophilicity (omega), and the difference in global electrophilicity (Deltaomega) between the reacting pairs and Fukui functions (f (+) and f(-)). The results revealed that s-trans is the predominant conformation of azadienes at ambient temperature and the barrier for conversion of the s-trans rotamer of 1-azadienes to s-cis may be the major factor influencing the chemoselectivity, i.e., [4+2] verses [2+2] cycloaddition. The regiochemistry of the observed cycloadditions is collated with the obtained local electrophilicity indices (Fukui functions). Transition states for the formation of both [4+2] and [2+2] cycloadducts as located at the PM3 level indicate that the transition state for the formation of [4+2] cycloadducts has lower energy, again supporting the earlier conclusion that preferred formation of [4+2] cycloaaducts at higher temperature may be a consequence of barrier for s-trans to s-cis transformation of 1-azadienes.

  18. 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.

  19. Novel Synthesis of 1,2,3-Triazoles via 1,3-Dipolar Cycloadditions of Alkynes to Azides in Ionic Liquid

    Institute of Scientific and Technical Information of China (English)

    ZHONG,Ping(钟平); GUO,Sheng-Rong(郭圣荣)

    2004-01-01

    2-Azido-3,5-dichloropyridine and 2-azido-5-chloro-3-fluoropyridine were given by reaction of sodium azide with 2,3,5-trichloropyridine, 3,5-dichloro-2-fluoropyridine or 5-chloro-2,3-difiuoropyridine in ionic liquids.1,3-Dipolar cycloaddition of 2-azido-3,5-dichloropyridine or 2-azido-5-chloro-3-fluoropyridine to alkynes in ionic liquids afforded the corresponding 1,4,5-trisubstituted [1,2,3]-triazoles in good yields and regioselectivities.

  20. Azide-enolate 1,3-dipolar cycloaddition in the synthesis of novel triazole-based miconazole analogues as promising antifungal agents.

    Science.gov (United States)

    González-Calderón, Davir; Mejía-Dionicio, María G; Morales-Reza, Marco A; Ramírez-Villalva, Alejandra; Morales-Rodríguez, Macario; Jauregui-Rodríguez, Bertha; Díaz-Torres, Eduardo; González-Romero, Carlos; Fuentes-Benítes, Aydeé

    2016-04-13

    Seven miconazole analogs involving 1,4,5-tri and 1,5-disubstituted triazole moieties were synthesized by azide-enolate 1,3-dipolar cycloaddition. The antifungal activity of these compounds was evaluated in vitro against four filamentous fungi, including Aspergillus fumigatus, Trichosporon cutaneum, Rhizopus oryzae, and Mucor hiemalis as well as three species of Candida spp. as yeast specimens. These pre-clinical studies suggest that compounds 4b, 4d and 7b can be considered as drug candidates for future complementary biological studies due to their good/excellent antifungal activities.

  1. Bifunctional Imidazolium-Based Ionic Liquid Decorated UiO-67 Type MOF for Selective CO2 Adsorption and Catalytic Property for CO2 Cycloaddition with Epoxides.

    Science.gov (United States)

    Ding, Luo-Gang; Yao, Bing-Jian; Jiang, Wei-Ling; Li, Jiang-Tao; Fu, Qi-Juan; Li, Yan-An; Liu, Zhen-Hua; Ma, Jian-Ping; Dong, Yu-Bin

    2017-02-20

    A bifunctional robust and highly porous imidazolium-based ionic liquid decorated UiO-67 type MOF (UiO-67-IL, 1) was successfully constructed via solvothermal assembly of the imidazolium-based ligand and Zr(IV) ions. It exhibits a highly selective adsorption for CO2 over CH4 and N2. Furthermore, 1 herein can be used as a highly active heterogeneous catalyst for CO2 cycloaddition with epoxides under atmospheric pressure with or without cocatalyst TBAB (n-Bu4NBr).

  2. 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.

  3. 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.

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

    Science.gov (United States)

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

    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 bitriazoles and the related CuAAAC reaction in different fields, including medicinal chemistry, coordination chemistry, biochemistry, and supramolecular chemistry, have been highlighted.

  5. Gold-Catalyzed β-Regioselective Formal [3 + 2] Cycloaddition of Ynamides with Pyrido[1,2-b]indazoles: Reaction Development and Mechanistic Insights.

    Science.gov (United States)

    Yu, Yinghua; Chen, Gui; Zhu, Lei; Liao, Yun; Wu, Yufeng; Huang, Xueliang

    2016-09-16

    Here, we report an unprecedented gold(I)-induced β-site regioselective formal [3 + 2] cycloaddition of ynamides with pyrido[1,2-b]indazoles, giving 3-amido-7-(pyrid-2'-yl)indoles in good to excellent yields. A complex of gold(I) catalyst with ynamide was isolated and characterized by X-ray diffraction analysis for the first time. Mechanistic investigations suggest the reaction pathway involves a gold-stabilized carbocation intermediate, which in turn participated in sequential C-H bond functionalization of the ortho-position of the phenyl ring.

  6. 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

  7. Periselectivity switch of acylketenes in cycloadditions with 1-azadienes: microwave-assisted diastereoselective domino three-component synthesis of α-spiro-δ-lactams.

    Science.gov (United States)

    Presset, Marc; Coquerel, Yoann; Rodriguez, Jean

    2010-09-17

    The microwave-assisted Wolff rearrangement of cyclic 2-diazo-1,3-diketones in the presence of primary amines and α,β-unsaturated aldehydes provides a straightforward three-component stereoselective access to a variety of α-spiro-δ-lactams following an imination/Wolff rearrangement/[2 + 4] cycloaddition domino sequence. With aniline derivatives, a complementary aza-Wittig/Wolff rearrangement/[2 + 4] sequence was developed. These reactions feature an unprecedented reactivity of acylketenes as dienophiles in 6π electrocyclic processes.

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

    Science.gov (United States)

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

    2016-03-04

    The CuI- or Ag₂CO₃-catalyzed [3+2] cycloaddition of propargyl-substituted dihydroisoindolin-1-one (3) with arylnitrile oxides 1a-d (Ar = Ph, p-MeC₆H₄, p-MeOC₆H₄, p-ClC₆H₄) produces in good yields novel 3,5-disubstituted isoxazoles 4 of the ethyl-2-benzyl-3-oxo-1-((3-arylisoxazol-5yl)methyl)-2,3-dihydro-1H-isoindole-1-carboxylate type. With aryl azides 2a-d (Ar = Ph, p-MeC₆H₄, p-OMeC₆H₄, p-ClC₆H₄), a series of 1,4-disubstituted 1,2,3-triazoles 6 (ethyl-2-benzyl-3-oxo-1-((1-aryl-1H-1,2,3-triazol-4-yl)methyl)-2,3-dihydro-1H-isoindole-1-carboxylates) was obtained. The reactions proceed in a regioselective manner affording exclusively racemic adducts 4 and 6. Compared to the uncatalyzed cycloaddition, the yields are significantly improved in the presence of CuI as catalyst, without alteration of the selectivity. The regio- and stereochemistry of the cycloadducts has been corroborated by an X-ray diffraction study of 4a, and in the case of 6a by XH-correlation and HMBC spectra.

  9. 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.

  10. 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).

  11. 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.

  12. A theoretical study on the reaction pathways and the mechanism of 1,3- dipolar cycloaddition of vinyl acetylene and methyl azide.

    Science.gov (United States)

    Siadati, Seyyed Amir; Mahboobifar, Ali; Nasiri, Ramin

    2014-01-01

    1,3-dipolar cycloaddition procedure is one of the most widely practiced methods in order to synthesize heterocyclic compounds. Although, it seems very simple, but, there are numerous precursors of heterocyclic molecules who have more than one positions to react with a 1,3-dipole species. As a result, while using a precursor with more than one position for reaction, it is probable to synthesize several products with different structures. This paper studies all possible interactions of vinyl acetylene, which has two positions for reaction, with methyl azide. This reaction could lead to the emergence of any 1,3-dipolar cycloaddition products. Our ultimate goal is to help researchers to find out how precursors containing both carbon-carbon double, and the triple bonds interact with 1,3- dipolar species. The present study used the DFT calculations at B3LYP/6-311++G(3df,pd) level to check all probable interactions between vinyl acetylene and methyl azide, and determined Potential Energy Surface, and optimized all species.

  13. 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.

  14. [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.

  15. 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...

  16. 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.

  17. Total abdominal colectomy

    Science.gov (United States)

    ... the rectum. This can cause an infection or abscess. Scarring of the connection between the small intestine ... More Crohn disease Ileostomy Total proctocolectomy and ileal - anal pouch Total proctocolectomy with ileostomy Ulcerative colitis Patient ...

  18. Total parenteral nutrition - infants

    Science.gov (United States)

    ... medlineplus.gov/ency/article/007239.htm Total parenteral nutrition - infants To use the sharing features on this page, please enable JavaScript. Total parenteral nutrition (TPN) is a method of feeding that bypasses ...

  19. 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) is a method of feeding that bypasses ...

  20. 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....

  1. Reemplazo total de cadera

    OpenAIRE

    Sánchez Vergel, Alfredo; Fundación Valle de Lili

    2002-01-01

    Definición/Tipos de prótesis/ ¿Qué pacientes se podrían beneficiar de un reemplazo total de cadera?/Artrosis de cadera/Tipos de artrosis de cadera/Alternativas al reemplazo total de cadera/Preguntas frecuentes sobre el reemplazo total de cadera.

  2. 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...

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Rhodium(III)-catalyzed N-nitroso-directed C-H addition to ethyl 2-oxoacetate for cycloaddition/fragmentation synthesis of indazoles.

    Science.gov (United States)

    Chen, Jinsen; Chen, Pei; Song, Chao; Zhu, Jin

    2014-10-27

    Rh(III) -catalyzed N-nitroso-directed CH addition to ethyl 2-oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N-nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful CH functionalization-based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tricyclic-fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles.

  10. 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

  11. 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.

  12. 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 ...

  13. 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...

  14. Laparoscopic total pancreatectomy

    Science.gov (United States)

    Wang, Xin; Li, Yongbin; Cai, Yunqiang; Liu, Xubao; Peng, Bing

    2017-01-01

    Abstract Rationale: Laparoscopic total pancreatectomy is a complicated surgical procedure and rarely been reported. This study was conducted to investigate the safety and feasibility of laparoscopic total pancreatectomy. Patients and Methods: Three patients underwent laparoscopic total pancreatectomy between May 2014 and August 2015. We reviewed their general demographic data, perioperative details, and short-term outcomes. General morbidity was assessed using Clavien–Dindo classification and delayed gastric emptying (DGE) was evaluated by International Study Group of Pancreatic Surgery (ISGPS) definition. Diagnosis and Outcomes: The indications for laparoscopic total pancreatectomy were intraductal papillary mucinous neoplasm (IPMN) (n = 2) and pancreatic neuroendocrine tumor (PNET) (n = 1). All patients underwent laparoscopic pylorus and spleen-preserving total pancreatectomy, the mean operative time was 490 minutes (range 450–540 minutes), the mean estimated blood loss was 266 mL (range 100–400 minutes); 2 patients suffered from postoperative complication. All the patients recovered uneventfully with conservative treatment and discharged with a mean hospital stay 18 days (range 8–24 days). The short-term (from 108 to 600 days) follow up demonstrated 3 patients had normal and consistent glycated hemoglobin (HbA1c) level with acceptable quality of life. Lessons: Laparoscopic total pancreatectomy is feasible and safe in selected patients and pylorus and spleen preserving technique should be considered. Further prospective randomized studies are needed to obtain a comprehensive understanding the role of laparoscopic technique in total pancreatectomy. PMID:28099344

  15. 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

  16. 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.)

  17. 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...

  18. 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...

  19. 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.

  20. 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

  1. Aryne [3 + 2] cycloaddition with N-sulfonylpyridinium imides and in situ generated N-sulfonylisoquinolinium imides: a potential route to pyrido[1,2-b]indazoles and indazolo[3,2-a]isoquinolines.

    Science.gov (United States)

    Zhao, Jingjing; Li, Pan; Wu, Chunrui; Chen, Hongli; Ai, Wenying; Sun, Renhong; Ren, Hailong; Larock, Richard C; Shi, Feng

    2012-03-07

    The aryne [3 + 2] cycloaddition process with pyridinium imides breaks the aromaticity of the pyridine ring. By equipping the imide nitrogen with a sulfonyl group, the intermediate readily eliminates a sulfinate anion to restore the aromaticity, leading to the formation of pyrido[1,2-b]indazoles. The scope and limitation of this reaction are discussed. As an extension of this chemistry, N-tosylisoquinolinium imides, generated in situ from N'-(2-alkynylbenzylidene)-tosylhydrazides via an AgOTf-catalyzed 6-endo-dig electrophilic cyclization, readily undergo aryne [3 + 2] cycloaddition to afford indazolo[3,2-a]-isoquinolines in the same pot, offering a highly efficient route to these potential anticancer agents.

  2. 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...

  3. 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.

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

    Directory of Open Access Journals (Sweden)

    Chisato Mukai

    2011-04-01

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

  5. 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...

  6. 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...

  7. 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 milligrams per deciliter (mg/dL) ...

  8. 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.

  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 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...

  11. 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…

  12. 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…

  13. Thinking out of the black box: accurate barrier heights of 1,3-dipolar cycloadditions of ozone with acetylene and ethylene.

    Science.gov (United States)

    Wheeler, Steven E; Ess, Daniel H; Houk, K N

    2008-02-28

    Accurate barriers for the 1,3-dipolar cycloadditions of ozone with acetylene and ethylene have been determined via the systematic extrapolation of ab initio energies within the focal point approach of Allen and co-workers. Electron correlation has been accounted for primarily via coupled cluster theory, including single, double, and triple excitations, as well as a perturbative treatment of connected quadruple excitations [CCSD, CCSD(T), CCSDT, and CCSDT(Q)]. For the concerted [4 + 2] cycloadditions, the final recommended barriers are DeltaH(0K) = 9.4 +/- 0.2 and 5.3 +/- 0.2 kcal mol(-1) for ozone adding to acetylene and ethylene, respectively. These agree with recent results of Cremer et al. and Anglada et al., respectively. The reaction energy for O3 + C2H2 exhibits a protracted convergence with respect to inclusion of electron correlation, with the CCSDT/cc-pVDZ and CCSDT(Q)/cc-pVDZ values differing by 2.3 kcal mol-1. Recommended enthalpies of formation (298 K) for cycloadducts 1,2,3-trioxole and 1,2,3-trioxolane are +32.8 and -1.6 kcal mol(-1), respectively. Popular composite ab initio approaches [CBS-QB3, CBS-APNO, G3, G3B3, G3(MP2)B3, G4, G4(MP3), and G4(MP2)] predict a range of barrier heights for these systems. The CBS-QB3 computed barrier for ozone and acetylene, DeltaH(0K) = 4.4 kcal mol(-1), deviates by 5 kcal mol(-1) from the focal point value. CBS-QB3 similarly underestimates the barrier for the reaction of ozone and ethylene, yielding a prediction of only 0.7 kcal mol(-1). The errors in the CBS-QB3 results are significantly larger than mean errors observed in application to the G2 test set. The problem is traced to the nontransferability of MP2 basis set effects in the case of these reaction barriers. The recently published G4 and G4(MP2) approaches perform substantially better for O3 + C2H2, predicting enthalpy barriers of 9.0 and 8.4 kcal mol(-1), respectively. For the prediction of these reaction barriers, the additive corrections applied in the

  14. 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.

  15. 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...

  16. Total Synthesis of (-)-Conolutinine.

    Science.gov (United States)

    Feng, Xiangyang; Jiang, Guangde; Xia, Zilei; Hu, Jiadong; Wan, Xiaolong; Gao, Jin-Ming; Lai, Yisheng; Xie, Weiqing

    2015-09-18

    The first enantioselective synthesis of (-)-conolutinine was achieved in 10 steps. The synthesis featured a catalytic asymmetric bromocyclization of tryptamine to forge the tricycle intermediate. Hydration of an alkene catalyzed by Co(acac)2 was also employed as a key step to diastereoselectively introduce the tertiary alcohol moiety. The absolute configuration of (-)-conolutinine was established to be (2S,5aS,8aS,13aR) based on this asymmetric total synthesis.

  17. TOTAL PERFORMANCE SCORECARD

    OpenAIRE

    Anca ȘERBAN; Oana DUMITRAȘCU

    2013-01-01

    The purpose of this paper is to present the evolution of the Balanced Scorecard from a measurement instrument to a strategic performance management tool and to highlight the advantages of implementing the Total Performance Scorecard, especially for Human Resource Management. The study has been accomplished using the methodology of bibliographic study and various secondary sources. Implementing the classical Balanced Scorecard indicated over the years, repeatedly failure. It can be indicated t...

  18. 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.

  19. 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

  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.

  1. 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.

  2. Adhesion of photon-driven molecular motors to surfaces via 1,3-dipolar cycloadditions: effect of interfacial interactions on molecular motion.

    Science.gov (United States)

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

    2011-01-25

    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, and ellipsometry measurements. Surface-bound motors were found to undergo photochemical and thermal isomerizations consistent with unidirectional rotation in solution. Confinement at a surface was found to reduce the rate of the thermal isomerization process. The rate of thermal isomerization was also dependent on the surface coverage of the motors. In solution, changes in the UV-vis signal that accompany thermal isomerization can be fit with a single monoexponential decay. In contrast, thermal isomerization of the surface-bound motors does not follow a single monoexponential decay and was found to fit a biexponential decay. Both one- and two-legged motors were attached to surfaces. The kinetics of thermal isomerization was not affected by the valency of attachment, indicating that the changes in kinetics from solution to surface systems are related to interactions between the surface-bound motors.

  3. 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.

  4. Studies of nitrile oxide cycloadditions, and the phenolic oxidative coupling of vanillin aldoxime by Geobacillus sp. DDS012 from Italian rye grass silage.

    Science.gov (United States)

    Kelly, David R; Baker, Simon C; King, David S; de Silva, Deepa S; Lord, Gwyn; Taylor, Jason P

    2008-02-21

    During studies directed towards the discovery of nitrile hydrolysing enzymes from thermophiles, vanillin aldoxime was incubated with the thermophilic organism, Geobacillus sp. DDS012 isolated from Italian rye grass (Lolium multiflorum) silage. The predominant product was a dihydro-dimer, which could only be characterised by LC-MS. This was initially imagined to be the product of cycloaddition of vanillin aldoxime with the corresponding nitrile oxide, but preparation of the supposed adduct and model studies excluded this possibility. The rate constant for the second order dimerisation of 4-O-acetyl vanillin nitrile oxide was measured (1.21 x 10(-4) M(-1) s(-1), 0.413 M, 25 degrees C) and the (13)C-NMR signal for the nitrile oxide carbon was observed (delta(C) 34.4, br. t (1)J(13)C,(14)N circa 50 Hz). Treatment of vanillin aldoxime with potassium persulfate and iron sulfate gave material with the same LC-MS properties as the natural product, which is therefore identified as 5,5'-dehydro-di-(vanillin aldoxime) 1d formed by phenolic oxidative coupling.

  5. Healable capacitive touch screen sensors based on transparent composite electrodes comprising silver nanowires and a furan/maleimide diels-alder cycloaddition polymer.

    Science.gov (United States)

    Li, Junpeng; Liang, Jiajie; Li, Lu; Ren, Fengbo; Hu, Wei; Li, Juan; Qi, Shuhua; Pei, Qibing

    2014-12-23

    A healable transparent capacitive touch screen sensor has been fabricated based on a healable silver nanowire-polymer composite electrode. The composite electrode features a layer of silver nanowire percolation network embedded into the surface layer of a polymer substrate comprising an ultrathin soldering polymer layer to confine the nanowires to the surface of a healable Diels-Alder cycloaddition copolymer and to attain low contact resistance between the nanowires. The composite electrode has a figure-of-merit sheet resistance of 18 Ω/sq with 80% transmittance at 550 nm. A surface crack cut on the conductive surface with 18 Ω is healed by heating at 100 °C, and the sheet resistance recovers to 21 Ω in 6 min. A healable touch screen sensor with an array of 8×8 capacitive sensing points is prepared by stacking two composite films patterned with 8 rows and 8 columns of coupling electrodes at 90° angle. After deliberate damage, the coupling electrodes recover touch sensing function upon heating at 80 °C for 30 s. A capacitive touch screen based on Arduino is demonstrated capable of performing quick recovery from malfunction caused by a razor blade cutting. After four cycles of cutting and healing, the sensor array remains functional.

  6. Solid-state Photochemical [2+2] Cycloaddition Reaction of Hydrogen-Bonded Zn(II) Metal Complex Containing Several Parallel C=C Bonds

    Indian Academy of Sciences (India)

    ABDUL MALIK P PEEDIKAKKAL

    2017-02-01

    A 2D hydrogen-bonded dinuclear Zn(II) complex, [{Zn(H₂O) ₃ (bpe) ₂} ₂ (bpe)](NO₃) ₄・3bpe・14H₂O,1 (bpe = 4,4_-bipyridylethylene) containing coordination complex cations, [{Zn(H₂O) ₃ (bpe) ₂} ₂ (μ-bpe)] ⁴⁺and free bpe and lattice water molecules shows face-to-face, π ・ ・ ・ π stacking of two of the four free bpemolecules with coordinated bpe ligands. Out of eight bpe molecules, six are aligned in parallel fashion withshort C・ ・ ・ C distances of 3.663–3.814Å and they undergo photochemical [2+2] cycloaddition reaction. The photoreaction conducted on ground sample of 1 in the solid-state affords rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) product in 75% yield. The molecular movement of free bpe molecules was tested by conducting thephotoreaction in ground sample and heated sample of single crystals. The photoreactivity study of 1 indicates that the free bpe molecules are locked between the cationic [{Zn(H₂O) ₃ (bpe) ₂} ₂ (bpe)] ⁴⁺ layers.

  7. 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.

  8. 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.

    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.

  9. Primary total elbow arthroplasty

    Directory of Open Access Journals (Sweden)

    Suresh Kumar

    2013-01-01

    Full Text Available Background: Primary total elbow arthroplasty (TEA is a challenging procedure for orthopedic surgeons. It is not performed as frequently as compared to hip or knee arthroplasty. The elbow is a nonweight-bearing joint; however, static loading can create forces up to three times the body weight and dynamic loading up to six times. For elderly patients with deformity and ankylosis of the elbow due to posttraumatic arthritis or rheumatoid arthritis or comminuted fracture distal humerus, arthroplasty is one of the option. The aim of this study is to analyze the role of primary total elbow arthroplasty in cases of crippling deformity of elbow. Materials and Methods: We analyzed 11 cases of TEA, between December 2002 and September 2012. There were 8 females and 3 males. The average age was 40 years (range 30-69 years. The indications for TEA were rheumatoid arthritis, comminuted fracture distal humerus with intraarticular extension, and posttraumatic bony ankylosis of elbow joint. The Baksi sloppy (semi constrained hinge elbow prosthesis was used. Clinico-radiological followup was done at 1 month, 3 months, 6 months, 1 year, and then yearly basis. Results: In the present study, average supination was 70° (range 60-80° and average pronation was 70° (range 60-80°. Average flexion was 135° (range 130-135°. However, in 5 cases, there was loss of 15 to 35° (average 25° of extension (45° out of 11 cases. The mean Mayo elbow performance score was 95.4 points (range 70-100. Arm length discrepancy was only in four patients which was 36% out of 11 cases. Clinico-radiologically all the elbows were stable except in one case and no immediate postoperative complication was noted. Radiolucency or loosening of ulnar stem was seen in 2 cases (18% out of 11 cases, in 1 case it was noted after 5 years and in another after 10 years. In second case, revision arthroplasty was done, in which only ulnar hinge section, hinge screw and lock screw with hexagonal head

  10. 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.

  11. The total artificial heart.

    Science.gov (United States)

    Cook, Jason A; Shah, Keyur B; Quader, Mohammed A; Cooke, Richard H; Kasirajan, Vigneshwar; Rao, Kris K; Smallfield, Melissa C; Tchoukina, Inna; Tang, Daniel G

    2015-12-01

    The total artificial heart (TAH) is a form of mechanical circulatory support in which the patient's native ventricles and valves are explanted and replaced by a pneumatically powered artificial heart. Currently, the TAH is approved for use in end-stage biventricular heart failure as a bridge to heart transplantation. However, with an increasing global burden of cardiovascular disease and congestive heart failure, the number of patients with end-stage heart failure awaiting heart transplantation now far exceeds the number of available hearts. As a result, the use of mechanical circulatory support, including the TAH and left ventricular assist device (LVAD), is growing exponentially. The LVAD is already widely used as destination therapy, and destination therapy for the TAH is under investigation. While most patients requiring mechanical circulatory support are effectively treated with LVADs, there is a subset of patients with concurrent right ventricular failure or major structural barriers to LVAD placement in whom TAH may be more appropriate. The history, indications, surgical implantation, post device management, outcomes, complications, and future direction of the TAH are discussed in this review.

  12. On the Critical Effect of the Metal (Mo vs. W) on the [3+2] Cycloaddition Reaction of M3 S4 Clusters with Alkynes: Insights from Experiment and Theory.

    Science.gov (United States)

    Bustelo, Emilio; Gushchin, Artem L; Fernández-Trujillo, M Jesús; Basallote, Manuel G; Algarra, Andrés G

    2015-10-12

    Whereas the cluster [Mo3 S4 (acac)3 (py)3 ](+) ([1](+) , acac=acetylacetonate, py=pyridine) reacts with a variety of alkynes, the cluster [W3 S4 (acac)3 (py)3 ](+) ([2](+) ) remains unaffected under the same conditions. The reactions of cluster [1](+) show polyphasic kinetics, and in all cases clusters bearing a bridging dithiolene moiety are formed in the first step through the concerted [3+2] cycloaddition between the C≡C atoms of the alkyne and a Mo(μ-S)2 moiety of the cluster. A computational study has been conducted to analyze the effect of the metal on these concerted [3+2] cycloaddition reactions. The calculations suggest that the reactions of cluster [2](+) with alkynes feature ΔG(≠) values only slightly larger than its molybdenum analogue, however, the differences in the reaction free energies between both metal clusters and the same alkyne reach up to approximately 10 kcal mol(-1) , therefore indicating that the differences in the reactivity are essentially thermodynamic. The activation strain model (ASM) has been used to get more insights into the critical effect of the metal center in these cycloadditions, and the results reveal that the change in reactivity is entirely explained on the basis of the differences in the interaction energies Eint between the cluster and the alkyne. Further decomposition of the Eint values through the localized molecular orbital-energy decomposition analysis (LMO-EDA) indicates that substitution of the Mo atoms in cluster [1](+) by W induces changes in the electronic structure of the cluster that result in weaker intra- and inter-fragment orbital interactions.

  13. 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.

  14. Computational methods to calculate accurate activation and reaction energies of 1,3-dipolar cycloadditions of 24 1,3-dipoles.

    Science.gov (United States)

    Lan, Yu; Zou, Lufeng; Cao, Yang; Houk, K N

    2011-12-01

    Theoretical calculations were performed on the 1,3-dipolar cycloaddition reactions of 24 1,3-dipoles with ethylene and acetylene. The 24 1,3-dipoles are of the formula X≡Y(+)-Z(-) (where X is HC or N, Y is N, and Z is CH(2), NH, or O) or X═Y(+)-Z(-) (where X and Z are CH(2), NH, or O and Y is NH, O, or S). The high-accuracy G3B3 method was employed as the reference. CBS-QB3, CCSD(T)//B3LYP, SCS-MP2//B3LYP, B3LYP, M06-2X, and B97-D methods were benchmarked to assess their accuracies and to determine an accurate method that is practical for large systems. Several basis sets were also evaluated. Compared to the G3B3 method, CBS-QB3 and CCSD(T)/maug-cc-pV(T+d)Z//B3LYP methods give similar results for both activation and reaction enthalpies (mean average deviation, MAD, < 1.5 kcal/mol). SCS-MP2//B3LYP and M06-2X give small errors for the activation enthalpies (MAD < 1.5 kcal/mol), while B3LYP has MAD = 2.3 kcal/mol. SCS-MP2//B3LYP and B3LYP give the reasonable reaction enthalpies (MAD < 5.0 kcal/mol). The B3LYP functional also gives good results for most 1,3-dipoles (MAD = 1.9 kcal/mol for 17 common 1,3-dipoles), but the activation and reaction enthalpies for ozone and sulfur dioxide are difficult to calculate by any of the density functional methods.

  15. Microwave synthesis of mono- and bis-tetrazolato complexes via 1,3-dipolar cycloaddition of organonitriles with platinum(II)-bound azides.

    Science.gov (United States)

    Mukhopadhyay, Suman; Lasri, Jamal; Charmier, M Adília Januário; da Silva, M Fátima C Guedes; Pombeiro, Armando J L

    2007-12-07

    [2 + 3] Cycloaddition reactions of the diazidoplatinum(II) complexes cis-[Pt(N3)2(PPh3)2] 1 and cis-[Pt(N3)2(2,2'-bipy)] 4 with organonitriles NCR 2 give the bis(tetrazolato) complexes trans-[Pt(N4CR)2(PPh3)2] 3 [R = Me (3a), Et (3b), Pr (3c), Ph (3d), 4-ClC6H4 (3e)] and cis-[Pt(N4CR)2(2,2'-bipy)] 5 [R = Me (5a), Et (5b), Pr (5c), Ph (5d)]. The reaction of cis-[Pt(N3)2(PPh3)2] I with propionitrile also affords, apart from 3b, the unexpected mixed cyano-tetrazolato complex trans-[Pt(CN)(5-ethyltetrazolato)(PPh3)2] 3b' which is derived from the reaction of the bis(tetrazolato) 3b with propionitrile, with concomitant formation of 5-ethyl-1H-tetrazole, via a suggested unusual oxidative addition of the nitrile to PtII. All these reactions are greatly accelerated by microwave irradiation and this method also shows a higher selectivity in the case of the reaction of propionitrile with 1, leading only to the formation of 3b. All the complexes obtained were characterized by IR, 1H, 13C and 31P[1H] (for complexes 3) NMR spectroscopies, FAB-MS and elemental analyses. Complexes 3b', 3d, 3e and 5d were also characterized by X-ray structural analyses.

  16. Limiting nuclearity in formation of polynuclear metal complexes through [2 + 3] cycloaddition: synthesis and magnetic properties of tri- and pentanuclear metal complexes.

    Science.gov (United States)

    Saha, Manideepa; Nasani, Rajendar; Das, Mriganka; Mahata, Arup; Pathak, Biswarup; Mobin, Shaikh M; Carrella, Luca M; Rentschler, Eva; Mukhopadhyay, Suman

    2014-06-07

    A tridentate ligand p-chloro-2-{(2-(dimethylamino)ethylimino)methyl}phenol (HL) was used to generate an octahedral nickel complex [Ni(L)Cl(H2O)2] 1 which was further converted into a square-planar nickel complex [Ni(L)(N3)] 2. The [2 + 3] cycloaddition reaction between metal coordinated azide 2 and different organonitriles under microwave irradiation afforded tri- and pentanuclear nickel(II) complexes 4a-4c. Reaction with benzonitrile and 3-cyano pyridine furnished the trinuclear species [Ni3L2(5-phenyltetrazolato)4(DMF)2] 4a and [Ni3L2{5-(3-pyridyl)-tetrazolato}4(DMF)2]·2H2O 4b, respectively. The nickel centers were found to be linearly disposed to each other and the complex is formed by a 2,3-tetrazolate bridge and a phenoxo bridge between central and terminal nickel atoms. Compound 2 when treated with 1,2-dicyanobenzene under identical conditions furnished a pentanuclear complex [Ni5L4{5-(2-cyanophenyl)-tetrazolato}4(OH)2(H2O)2]·3H2O·DMF 4c. In this pentanuclear compound two dimeric nickel units are connected to the central nickel center by a μ3-hydroxo bridge and a tetrazolate ligand operating via a relatively rare 1,2,3-bridging mode. The compounds were characterized by IR, elemental analysis, thermogravimetric analysis and single crystal X-ray crystallography. The magnetic susceptibility data for compounds 4a-4c show dominant antiferromagnetic interactions between the nickel centers for all the complexes. DFT calculations were performed to investigate the magnetic parameter in one of the complexes 4b by a broken symmetry approach.

  17. Cycloaddition Reaction Mechanism between Dichloromethylene Germylene and Methanethial%二氯乙烯锗烯与甲硫醛环加成的反应机理

    Institute of Scientific and Technical Information of China (English)

    陈新; 李瑛

    2008-01-01

    利用MP2/6-311+G*方法计算了单线态二氯乙烯锗烯与甲硫醛的各种反应机理.计算结果表明两者之间的环加成反应具有很好的选择性,优势反应路径分为二步:首先两种反应物经过无能垒的放热反应形成中间体INT,然后INT经历过渡态TS3异构化为P31,最后P31继续与甲硫醛反应形成二环杂环化合物P33.其中第一步反应放热103.4 kJ·mol-1,后两步反应能垒分别为0.7和32.3 kJ·mol-1.%Theoretical calculations at MP2/6-311+G* level were employed to investigate various reaction mechanisms between singlet dichloromethylene germylene and methanethial.Calculation results indicate that the dominant reaction pathway for this reaction consists of three steps. The two reactants initially form an intermediate INT through a barrier-free exothermic reaction of 103.4 kJ·mol-1 This intermediate then isomerizes to P31 via a transition state TS3 with an energy barrier of 0.7 kJ·mol-1 P31 finally reacts with methanethial to form the germanic heteropolycyclic product P33 with an energy barrier of 32.3 kJ·mol-1 This cycloaddition reaction thus has excellent selectivity.

  18. 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.

  19. A Theoretical Study of the Relationship between the Electrophilicity ω Index and Hammett Constant σp in [3+2] Cycloaddition Reactions of Aryl Azide/Alkyne Derivatives

    Directory of Open Access Journals (Sweden)

    Hicham Ben El Ayouchia

    2016-10-01

    Full Text Available The relationship between the electrophilicity ω index and the Hammett constant σp has been studied for the [2+3] cycloaddition reactions of a series of para-substituted phenyl azides towards para-substituted phenyl alkynes. The electrophilicity ω index—a reactivity density functional theory (DFT descriptor evaluated at the ground state of the molecules—shows a good linear relationship with the Hammett substituent constants σp. The theoretical scale of reactivity correctly explains the electrophilic activation/deactivation effects promoted by electron-withdrawing and electron-releasing substituents in both azide and alkyne components.

  20. An investigation of the Lewis acid mediated 1,3-dipolar cycloaddition between N-benzyl-C-(2-pyridyl)nitrone and allylic alcohol. Direct entry to isoxazolidinyl C-nucleosides.

    Science.gov (United States)

    Merino, Pedro; Tejero, Tomas; Laguna, Mariano; Cerrada, Elena; Moreno, Ana; Lopez, Jose A

    2003-07-07

    The cycloaddition reaction of N-benzyl C-(2-pyridyl) nitrone with allylic alcohol has been carried out to obtain the corresponding 2-benzyl-3-(2-pyridyl)-5-hydroxymethylisoxazolidine. The influence of Lewis acids in the reaction has been studied and a complete 3,5-regioselectivity and cis diastereoselectivity was observed when the reaction was carried out with 1.0 equiv of AgOTf, [Ag(OClO3)(PPh2Me)] or Zn(OTf)2. Insight into the mechanism of the reaction has been obtained by isolating and characterizing (X-ray) the intermediate complexes. Also, a model based on both experimental and theoretical results is proposed.

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

    OpenAIRE

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

    2004-01-01

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

  2. Stereo-, Regio-, and Chemoselective [3 + 2]-Cycloaddition of (2E,4E)-Ethyl 5-(Phenylsulfonyl)penta-2,4-dienoate with Various Azomethine Ylides, Nitrones, and Nitrile Oxides: Synthesis of Pyrrolidine, Isoxazolidine, and Isoxazoline Derivatives and a Computational Study.

    Science.gov (United States)

    Sankar, Ulaganathan; Surya Kumar, Ch Venkata; Subramanian, V; Balasubramanian, K K; Mahalakshimi, S

    2016-03-18

    One-pot chemo-, regio-, and stereoselective synthesis of series of heterocyclic and spiroheterocyclic compounds was accomplished through mono- and bis[3 + 2]-cycloaddition reactions of (2E,4E)-ethyl 5-(phenylsulfonyl)penta-2,4-dienoate as a dipolarophile with azomethine ylides, nitrones, and nitrile oxides in good yields. The structures of the products were established by spectroscopic techniques as well as by single-crystal XRD study, and DFT calculations were performed to further understand the mechanism of this [3 + 2]-cycloaddition reaction.

  3. 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.

  4. Total synthesis of dihydrolysergic acid and dihydrolysergol: development of a divergent synthetic strategy applicable to rapid assembly of D-ring analogs

    Science.gov (United States)

    Lee, Kiyoun; Poudel, Yam B.; Glinkerman, Christopher M.; Boger, Dale L.

    2015-01-01

    The total syntheses of dihydrolysergic acid and dihydrolysergol are detailed based on a Pd(0)-catalyzed intramolecular Larock indole cyclization for the preparation of the embedded tricyclic indole (ABC ring system) and a subsequent powerful inverse electron demand Diels–Alder reaction of 5-carbomethoxy-1,2,3-triazine with a ketone-derived enamine for the introduction of a functionalized pyridine, serving as the precursor for a remarkably diastereoselective reduction to the N-methylpiperidine D-ring. By design, the use of the same ketone-derived enamine and a set of related complementary heterocyclic azadiene [4 + 2] cycloaddition reactions permitted the late stage divergent preparation of a series of alternative heterocyclic derivatives not readily accessible by more conventional approaches. PMID:26273113

  5. 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.

  6. Weak Total Resolvability In Graphs

    Directory of Open Access Journals (Sweden)

    Casel Katrin

    2016-02-01

    Full Text Available A vertex v ∈ V (G is said to distinguish two vertices x, y ∈ V (G of a graph G if the distance from v to x is di erent from the distance from v to y. A set W ⊆ V (G is a total resolving set for a graph G if for every pair of vertices x, y ∈ V (G, there exists some vertex w ∈ W − {x, y} which distinguishes x and y, while W is a weak total resolving set if for every x ∈ V (G−W and y ∈ W, there exists some w ∈ W −{y} which distinguishes x and y. A weak total resolving set of minimum cardinality is called a weak total metric basis of G and its cardinality the weak total metric dimension of G. Our main contributions are the following ones: (a Graphs with small and large weak total metric bases are characterised. (b We explore the (tight relation to independent 2-domination. (c We introduce a new graph parameter, called weak total adjacency dimension and present results that are analogous to those presented for weak total dimension. (d For trees, we derive a characterisation of the weak total (adjacency metric dimension. Also, exact figures for our parameters are presented for (generalised fans and wheels. (e We show that for Cartesian product graphs, the weak total (adjacency metric dimension is usually pretty small. (f The weak total (adjacency dimension is studied for lexicographic products of graphs.

  7. 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.

  8. Total parenteral nutrition in children.

    Science.gov (United States)

    Zlotkin, S H; Stallings, V A; Pencharz, P B

    1985-04-01

    This article first focuses on the indications for total parenteral nutrition and the effect of its use on the outcome of various nutrient-depleting diseases in infants and children. This is followed by a discussion of some of the newer nutrient additions to total parenteral nutrition regimens, such as biotin, carnitine, zinc, copper, iron, and others.

  9. 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...

  10. 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

  11. Facile, regioselective [4 + 2] cycloaddition involving 1-aryl-4-phenyl-1-azadienes and allenic esters: an efficient route to novel substituted 1-aryl-4-phenyl-1,4-dihydropyridines.

    Science.gov (United States)

    Ishar, M P; Kumar, K; Kaur, S; Kumar, S; Girdhar, N K; Sachar, S; Marwaha, A; Kapoor, A

    2001-07-12

    [reaction: see text]1-Aryl-4-phenyl-1-azadienes undergo facile, regioselective [4 + 2] cycloaddition to the C2,C3 pi-bond of allenic esters in refluxing benzene, and the formed adducts undergo a 1,3-H shift to afford novel 2-alkyl-1-aryl-3-ethoxycarbonyl-4-phenyl-1,4-dihydropyridines (78-97%). However, when the reaction is carried at room temperature, besides the [4 + 2] addition, the [2 + 2] mode of addition involving C=N of azadiene and C3,C4 pi-bond of allenic esters also intervenes. The resulting N-aryl-2-ethoxy-carbonyl-methylidene-4-styrylazetidines (17-28%) undergo reorganization on silica gel to afford 2-cyclohexen-1-ones.

  12. 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...

  13. 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

  14. The total synthesis of psymberin.

    Science.gov (United States)

    Huang, Xianhai; Shao, Ning; Palani, Anandan; Aslanian, Robert; Buevich, Alexei

    2007-06-21

    The total synthesis of a new member of the pederin family of natural products, psymberin 1, was accomplished. Using a recently reported novel and efficient PhI(OAc)2 mediated oxidative entry to 2-(N-acylaminal)-substituted tetrahydropyrans as the key step, this total synthesis was executed in a convergent and efficient manner. The longest linear sequence of this synthesis was 22 steps starting from known 6.

  15. Total eclipses of the sun.

    Science.gov (United States)

    Zirker, J B

    1980-12-19

    Total eclipses of the sun offer research opportunities in a variety of sciences. Some of the advances in solar physics resulting from eclipse observations are discussed. Experiments at the total eclipse of 16 February 1980 in India are also described. These included a test of general relativity, studies in coronal physics, investigations of solar prominences, diameter measurements, a search for interplanetary dust, a study of the gravity waves in the earth's atmosphere, and experiments on the biological effects on animals and humans.

  16. 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.

  17. A computational study on the N-heterocyclic carbene-catalyzed Csp(2)-Csp(3) bond activation/[4+2] cycloaddition cascade reaction of cyclobutenones with imines: a new application of the conservation principle of molecular orbital symmetry.

    Science.gov (United States)

    Wang, Yang; Wu, Bohua; Zhang, Haoyang; Wei, Donghui; Tang, Mingsheng

    2016-07-20

    A comprehensive density functional theory (DFT) investigation has been performed to interrogate the mechanisms and stereoselectivities of the Csp(2)-Csp(3) single bond activation of cyclobutenones and their [4+2] cycloaddition reaction with imines via N-heterocyclic carbene (NHC) organocatalysis. According to our calculated results, the fundamental reaction pathway contains four steps: nucleophilic addition of NHC to cyclobutenone, C-C bond cleavage for the formation of an enolate intermediate, [4+2] cycloaddition of the enolate intermediate with isatin imine, and the elimination of the NHC catalyst. In addition, the calculated results also reveal that the second reaction step is the rate-determining step, whereas the third step is the regio- and stereo-selectivity determining step. For the regio- and stereo-selectivity determining step, all four possible attack modes were considered. The addition of the C[double bond, length as m-dash]N bond in isatin imine to the dienolate intermediate is more energy favorable than the addition of the C[double bond, length as m-dash]O bond to a dienolate intermediate. Moreover, the Re face addition of the C[double bond, length as m-dash]N bond in isatin imine to the Re face of the dienolate intermediate leading to the SS configuration N-containing product was demonstrated to be most energy favorable, which is mainly due to the stronger second-order perturbation energy value in the corresponding transition state. Furthermore, by tracking the frontier molecular orbital (FMO) changes in the rate-determining C-C bond cleavage step, we found that the reaction obeys the conservation principle of molecular orbital symmetry. We believe that the present work would provide valuable insights into this kind of reaction.

  18. Total hip and total knee replacement: preoperative nursing management.

    Science.gov (United States)

    Lucas, Brian

    Total hip replacement (THR) and total knee replacement (TKR) surgery are carried out for the relief of hip or knee pain, usually caused by osteoarthritis. This is the first of two articles on THR and TKR. It will outline the different types of replacement used in lower limb joint replacement surgery. Preparation of patients for surgery requires attention to physical, psychological and social factors and these are explored in detail. The organization of services along the patient pathway to ensure comprehensive preparation is considered and the nursing role highlighted. The second article, to be published in the next issue, will discuss recovery and rehabilitation from THR and TKR surgery.

  19. 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.)

  20. 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.

  1. Total Ozone Prediction: Stratospheric Dynamics

    Science.gov (United States)

    Jackman, Charles H.; Kawa, S. Ramdy; Douglass, Anne R.

    2003-01-01

    The correct prediction of total ozone as a function of latitude and season is extremely important for global models. This exercise tests the ability of a particular model to simulate ozone. The ozone production (P) and loss (L) will be specified from a well- established global model and will be used in all GCMs for subsequent prediction of ozone. This is the "B-3 Constrained Run" from M&MII. The exercise mostly tests a model stratospheric dynamics in the prediction of total ozone. The GCM predictions will be compared and contrasted with TOMS measurements.

  2. 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].

  3. Qualidade total e cultura organizacional

    OpenAIRE

    Machado, Denise Del Pra Netto

    1996-01-01

    Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro Socio-Economico O ambiente dinâmico em que as organizações estão inseridas determina uma constante busca de competitividade. Com a adoção da Qualidade Total, como um processo ofensivo de enfrentamento das exigências de mercado, procura-se uma vantagem competitiva, além da sobrevi-vência organizacional. Com base no referencial teórico-empírico sobre Qualidade Total e Cultura Organizacional, procurou-se verifi-car o efei...

  4. VOICE REHABILITATION FOLLOWING TOTAL LARYNGECTOMY

    Directory of Open Access Journals (Sweden)

    Balasubramanian Thiagarajan

    2015-03-01

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

  5. Total enantioselective synthesis of (-)-cytisine.

    Science.gov (United States)

    Danieli, Bruno; Lesma, Giordano; Passarella, Daniele; Sacchetti, Alessandro; Silvani, Alessandra; Virdis, Andrea

    2004-02-19

    [reaction: see text] The first total enantiosynthesis of the biologically active alkaloid (-)-cytisine is reported, featuring a ruthenium-catalyzed RCM reaction as the key step. The approach relies on readily available cis-piperidine-3,5-dimethanol monoacetate as the chiral building block, and it is suited for achieving the target compound in both enantiomeric forms.

  6. Subtotal versus total abdominal hysterectomy

    DEFF Research Database (Denmark)

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

    2015-01-01

    a multiple imputation analysis, this difference disappeared (relative risk, 1.36; 95% confidence interval, 0.86-2.13; P = .19). No differences were seen in any of the secondary outcomes. CONCLUSION: Subtotal abdominal hysterectomy was not superior to total abdominal hysterectomy on any outcomes. More women...

  7. Spraakrevalidatie na een totale laryngectomie

    NARCIS (Netherlands)

    Timmermans, A.J.; Krap, M.; Hilgers, F.J.M.; van den Brekel, M.W.M.

    2012-01-01

    In patients with advanced laryngeal or hypopharyngeal cancer, or in cases when the disease recurs after treatment with (chemo)radiation, a total laryngectomy (TLE) is performed. For them to be able to function properly, speech rehabilitation is of the utmost importance for these patients. For voice

  8. [Hypoparathyroid risk after total thyroidectomy].

    Science.gov (United States)

    Milone, Antonino; Carditello, Antonio; Stilo, Francesco; Paparo, Domenica; Paparo, Teresa

    2004-01-01

    From January 1970 to December 1999, 881 patients with thyroid pathology underwent surgery consisting in 551 subtotal thyroidectomies and 330 total thyroidectomies. Permanent hypocalcaemia was present in 32 patients (3.6%). The importance of accurate isolation and ultraligature of the branches of the inferior thyroid artery in the prevention of parathyroid damage is stressed.

  9. Total Phenolics and Total Flavonoids in Selected Indian Medicinal Plants

    OpenAIRE

    C T Sulaiman; Indira Balachandran

    2012-01-01

    Plant phenolics and flavonoids have a powerful biological activity, which outlines the necessity of their determination. The phenolics and flavonoids content of 20 medicinal plants were determined in the present investigation. The phenolic content was determined by using Folin-Ciocalteu assay. The total flavonoids were measured spectrophotometrically by using the aluminium chloride colorimetric assay. The results showed that the family Mimosaceae is the richest source of phenolics, (Acacia ni...

  10. Synthesis and characterization of cyclic polystyrene using copper-catalyzed alkyne-azide cycloaddition coupling - evaluation of physical properties and optimization of cyclization conditions

    Science.gov (United States)

    Elupula, Ravinder

    . Whereas, anionically prepared A-PS had much higher reliance on the molecular weight changes for its glass transition temperature. However, in thin films, c-PS films have, within error, no confinement effect. In contrast, A-PS has seen large T g reduction with confinement. Ellipsometry analysis suggests that this invariance of the Tg-confinement effect in c-PS is a result of the weak perturbation to Tg near the free surface (i.e. the polymer-air interface). These weak perturbations are the result of the high packing efficiency of cyclic PS segments. The copper-catalyzed alkyne/azide cycloaddition (CuAAC) click reaction has been used to cyclize many linear polymers with complementary azide and alkyne end groups via unimolecular heterodifunctional approach. Cyclic polymers exhibit unique and potentially useful physical properties compared to their linear analogs, hence increasing interest in techniques for preparing this class of polymers. However, a general route for producing high purity cyclic polymers remained elusive. Prior to the discovery of "click" chemistry, it was difficult to produce highly pure cyclic polymers via the ring-closure approach, requiring extensive post-cyclization purification. However, even minor amounts of linear impurities can influence the physical properties of cyclic polymers. Thermal gradient interaction chromatography (TGIC) coupled with Matrix-Assisted Laser Desorption/Ionization Time of Flight Mass Spectrometry (MALDI-ToF MS) allows the fractionation of cyclic polymer samples and produce valuable data for determining both the quantity and identity of linear impurities. This understanding further enables us to optimize cyclization conditions towards the goal of and efficient, general methodology for producing highly pure cyclic polymers. To solve the ever-growing energy needs of the world and capture the renewable energy that is generated sporadically, we need to create devices that can store high amounts of energy and discharge power at

  11. 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.

  12. Rehabilitation for total joint arthroplasty.

    Science.gov (United States)

    Ritterman, Scott; Rubin, Lee E

    2013-05-01

    Total hip and knee replacement are two of the most common and successful elective surgeries preformed in the United States each year. Preoperative medical preparation and postoperative rehabilitation are equally important to a successful outcome. Physical deconditioning, tobacco use, obesity and medical co-morbidities can adversely affect outcomes and should be addressed before any elective procedure. Formal postoperative therapy is geared towards the specific surgery and is aimed at returning the patient to independent activity.

  13. Edge adaptive directional total variation

    Directory of Open Access Journals (Sweden)

    Hua Zhang

    2013-11-01

    Full Text Available The directional total variation (DTV model has been proposed very recently for image denoising. However, the DTV model works well when there is just one dominant direction in the image. In this Letter, the authors propose to make the DTV model adaptive to image edge direction so that the proposed model can handle images with several dominant directions. Experiment and comparison show the effectiveness of the proposed method.

  14. Total Monomeric Anthocyanin and Total Flavonoid Content of Processed Purple

    Directory of Open Access Journals (Sweden)

    Potato Florentina Damşa

    2016-01-01

    Full Text Available It is well known that processing change physical and chemical composition of foods, thus affecting the content in bioactive substances. Potatoes are almost always consumed after processing (baked, fried or boiled making it critical to understand the effect of such processing techniques on the containing in bioactive compounds. In order to determine the influence of processing on the content of anthocyanin pigments and flavonoids was achieved the extraction of these compounds from boiled and baked purple potato tuber (Albastru-Violet de Galanesti variety. Also, in order to obtain the maximum amount of anthocyanin pigments and flavonoids from processed potatoes was applied ultrasonic extraction (20 kHz and was performed the mathematical modeling (central composite design using SigmaXL software. The total anthocyanins content were determined spectrophotometrically by the pH differential method and the total flavonoids content were determine colorimetric by AlCl3 method. This study proves that the potato processing decreases the content of anthocyanin pigments and flavonoids.

  15. 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.

  16. 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.

  17. Diverticulosis in total colonic aganglionosis

    Energy Technology Data Exchange (ETDEWEB)

    Ivancev, K.; Fork, T.; Haegerstrand, I.; Ivarsson, S.; Kullendorff, C.M.

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

  18. Radiology of total hip replacement

    Energy Technology Data Exchange (ETDEWEB)

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

    1984-06-01

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

  19. 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.

  20. 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

  1. 'Total IBA' - Where are we?

    Energy Technology Data Exchange (ETDEWEB)

    Jeynes, C., E-mail: c.jeynes@surrey.ac.uk [University of Surrey Ion Beam Centre, Guildford (United Kingdom); Bailey, M.J.; Bright, N.J.; Christopher, M.E.; Grime, G.W.; Jones, B.N.; Palitsin, V.V.; Webb, R.P. [University of Surrey Ion Beam Centre, Guildford (United Kingdom)

    2012-01-15

    The suite of techniques which are available with the small accelerators used for MeV ion beam analysis (IBA) range from broad beams, microbeams or external beams using the various particle and photon spectrometries (including RBS, EBS, ERD, STIM, PIXE, PIGE, NRA and their variants), to tomography and secondary particle spectrometries like MeV-SIMS. These can potentially yield almost everything there is to know about the 3-D elemental composition of types of samples that have always been hard to analyse, given the sensitivity and the spacial resolution of the techniques used. Molecular and chemical information is available in principle with, respectively, MeV-SIMS and high resolution PIXE. However, these techniques separately give only partial information - the secret of 'Total IBA' is to find synergies between techniques used simultaneously which efficiently give extra information. We here review how far 'Total IBA' can be considered already a reality, and what further needs to be done to realise its full potential.

  2. "Total IBA" - Where are we?

    Science.gov (United States)

    Jeynes, C.; Bailey, M. J.; Bright, N. J.; Christopher, M. E.; Grime, G. W.; Jones, B. N.; Palitsin, V. V.; Webb, R. P.

    2012-01-01

    The suite of techniques which are available with the small accelerators used for MeV ion beam analysis (IBA) range from broad beams, microbeams or external beams using the various particle and photon spectrometries (including RBS, EBS, ERD, STIM, PIXE, PIGE, NRA and their variants), to tomography and secondary particle spectrometries like MeV-SIMS. These can potentially yield almost everything there is to know about the 3-D elemental composition of types of samples that have always been hard to analyse, given the sensitivity and the spacial resolution of the techniques used. Molecular and chemical information is available in principle with, respectively, MeV-SIMS and high resolution PIXE. However, these techniques separately give only partial information - the secret of "Total IBA" is to find synergies between techniques used simultaneously which efficiently give extra information. We here review how far "Total IBA" can be considered already a reality, and what further needs to be done to realise its full potential.

  3. 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.

  4. 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.

  5. Total hip replacement in dancers.

    Science.gov (United States)

    Buyls, Inge R A E; Rietveld, A B M Boni; Ourila, Tiia; Emerton, Mark E; Bird, H A

    2013-04-01

    A case report of a professional contemporary dancer who successfully returned to the stage after bilateral total hip replacements (THR) for osteoarthritis is presented, together with her own commentary and a retrospective cohort study of total hip replacements in dancers. In the presented cohort, there were no post-operative dislocations or infections, the original pain had been relieved, rehabilitation was objectively normal and all resumed their dance (teaching) activities. Nevertheless, they were disappointed about the prolonged rehabilitation. Due to their high demands as professional dancers, post-operative expectations were too optimistic in view of the usual quick and favourable results of THR in the older and less physically active, general population. In all dancers with unilateral osteoarthritis, the left hip was involved, which may reflect the tendency to use the left leg as standing leg and be suggestive that strenuous physical activity may lead to osteoarthritis. Better rehabilitation guidelines are needed for dancer patients undergoing THR, especially drawing their attention to realistic post-operative expectations.

  6. 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

  7. 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.

  8. 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.

  9. Total quality management program planning

    Energy Technology Data Exchange (ETDEWEB)

    Thornton, P.T.; Spence, K.

    1994-05-01

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

  10. 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.

  11. 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.

  12. 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.

  13. Total Petroleum Hydrocarbons (TPH): ToxFAQs

    Science.gov (United States)

    ... state: This map displays locations where Total Petroleum Hydrocarbons (TPH) is known to be present. On This ... get more information? ToxFAQs TM for Total Petroleum Hydrocarbons (TPH) ( Hidrocarburos Totales de Petróleo (TPH) ) August 1999 ...

  14. What Is a Total Artificial Heart?

    Science.gov (United States)

    ... the NHLBI on Twitter. What Is a Total Artificial Heart? A total artificial heart (TAH) is a device ... outside power source. Normal Heart and CardioWest Total Artificial Heart Figure A shows the normal structure and location ...

  15. Fusion following failed total ankle replacement.

    Science.gov (United States)

    Wünschel, Markus; Leichtle, Ulf G; Leichtle, Carmen I; Walter, Christian; Mittag, Falk; Arlt, Eva; Suckel, Andreas

    2013-04-01

    Although mid- to long-term results after total ankle replacement have improved because of available second- and third-generation devices, failure of total ankle replacement is still more common compared with total hip replacement and total knee replacement. The portfolio of available total ankle replacement revision component options is small. Furthermore, the bone stock of the tibiotalar region is scarce making it difficult and in some situations impossible to perform revision total ankle replacement. In these cases tibiotalar and tibiotalocalcaneal fusions are valuable options. This article describes which surgical procedures should be performed depending on the initial situation and gives detailed advice on surgical technique, postoperative care, and clinical results.

  16. 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.

  17. Total Productive Maintenance at Paccar INC

    OpenAIRE

    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.

  18. Total Productive Maintenance at Paccar INC

    Directory of Open Access Journals (Sweden)

    Ştefan Farkas

    2010-06-01

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

  19. Wear debris in cemented total hip arthroplasty.

    Science.gov (United States)

    Huo, M H; Salvati, E A; Buly, R L

    1991-03-01

    One of the most prevalent clinical problems in long-term follow up of total hip arthroplasty patients is loosening of prosthetic fixation. Factors contributing to mechanical failure of total hip reconstruction are complex and multiple. It has become increasingly apparent that wear debris from the prosthetic components may contribute significantly to this process. The authors summarize some of the current concepts concerning the detrimental effects of metallic debris in total hip arthroplasty.

  20. Total solar eclipse of 3 November 1994

    Science.gov (United States)

    Espenak, Fred; Anderson, Jay

    1993-01-01

    A total eclipse of the Sun will be visible from the southern half of the Western Hemisphere on 3 November 1994. The path of the Moon's shadow passes through Peru, Chile, Bolivia, Paraguay, and Brazil. Detailed predictions for this event are presented and include tables of geographic coordinates of the path of totality, local circumstances for hundreds of cities, maps of the path of total and partial eclipse, weather prospects, and the lunar limb profile.

  1. 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.

  2. 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.

  3. Total Formulates Aggressive Plan in China

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    @@ The world's fourth largest oil company Total is expanding its business in China's oil and gas exploration and production sector. Charles Mattenet, Total's senior vice president for Asia and the Far East, recently said in an interview with the news media that his company plans to start exploring in north China's Ordos Basin next year with its partner PetroChina. Total expects to invest60 million to 80 million U.S. dollars in its China project between 2007 and 2008, amounting for nearly 5 to 6percent of Total's worldwide budget for exploration and production.

  4. Metal complexes with 2,3-bis(diphenylphosphino)-1,4-diazadiene ligands: synthesis, structures, and an intramolecular metal-mediated [4 + 2] cycloaddition employing a benzene ring as a dienophile.

    Science.gov (United States)

    Walther, Dirk; Liesicke, Stefan; Böttcher, Lars; Fischer, Reinald; Görls, Helmar; Vaughan, Gavin

    2003-01-27

    2,3-Bis(diphenylphosphino)-1,4-diazadienes RN=C(PPh2)-C(PPh2)=NR (1a, R = 4-tolyl; 1b, R = 4-tert-butylphenyl; 1c, R = mesityl) were used as novel ligands for transition metals. The metal complexes [(1c)Mo(CO)4] (2a), [(1c)[Mo(CO)4]2] (2b), [(1a)Cu(Cl)(PPh3)] (3), and [(1b)[(NiBr2(THF))]2] (4) were characterized by elemental analysis, MS, and 31P[1H], 1H, and 13C NMR spectra (except the paramagnetic complex 4). Additionally, the molecular structure of the complexes in the solid state was determined by single-crystal X-ray diffraction. In 2a and 2b the chelating ligand coordinates via the N,P donor set, whereas in 3 the chelating ligand coordinates via the two P atoms. 4 contains a square-planar (P,P)NiBr2 moiety on the one side of the bridging ligand 1b. On the opposite side the 1,2-dimine unit bonds to another Ni center having octahedral geometry. The bulkier ligand 1c reacts to form the mononuclear compound 5. X-ray diffraction analysis of single crystals shows that 5 contains a quinoxaline derivative with a cyclohexa-1,3-diene ring in the peripheral position. Furthermore, it contains a bis(diphenylphosphino)-ethylene unit coordinating the NiBr2. This arrangement is the result of an intramolecular [4 + 2] cycloaddition between the 1,2-diimine unit (as diheterodiene) and the benzene ring of the 4-tolyl-N substituent (as dieneophile). The same type of ring-closing reaction followed by a tautomerization reaction to form the mononuclear compound 6 occurred by dissolution of the binuclear complex 4 in methanol. This reaction can be used as a simple method for the synthesis of novel 1,2-bis(diarylphosphanyl)ethylenes containing a quinoxaline backbone.

  5. 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.

  6. 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....

  7. EVALUATION OF TOTAL ORGANIC EMISSIONS ANALYSIS METHODS

    Science.gov (United States)

    The rationale and supporting experimental data for revising EPA's 1996 "Guidance for Total Organics" are summarized in this document. It reports the results of reseach and investigation of improvements to the Total Organic Emissions (TOE) guidance used by EPA to measure recovera...

  8. Airway Complications of Total Artificial Heart.

    Science.gov (United States)

    Pathak, Vikas; Donovan, Colin; Malhotra, Rajiv

    2017-02-01

    The total artificial heart is the mechanical device which is used as a bridge to the heart transplant in patients with biventricular failure. Due to the mechanical nature of the device, patients receiving total artificial heart (TAH) require to be on anticoagulation therapy. Hemorrhage and coagulopathy are few of the known complications of TAH.

  9. Total`s LNG activities from Algeria to Yemen; Total et le GNL de l`Algerie au Yemen

    Energy Technology Data Exchange (ETDEWEB)

    Vedrenne, J.P. [Compagnie de Raffinage et de Distribution TOTAL France, 75 - Paris (France)

    1997-05-01

    In March 1995, further to an international tender, Total was awarded the leadership of the first LNG project in Yemen. On January 1997 Total announced the extension of the share-holding of the Yemen LNG Co. to include the companies with interests in the Marib area (Hunt-Exxon-Yukong). The Marib area will supply the gas to the future liquefaction plant. The ratification of these agreements confirms the role of Total as lead shareholder with 36% in the share-holding structure and guarantees gas supply from the Marib licence, operated by Hunt-Exxon. (author).

  10. Totally optimal decision trees for Boolean functions

    KAUST Repository

    Chikalov, Igor

    2016-07-28

    We study decision trees which are totally optimal relative to different sets of complexity parameters for Boolean functions. A totally optimal tree is an optimal tree relative to each parameter from the set simultaneously. We consider the parameters characterizing both time (in the worst- and average-case) and space complexity of decision trees, i.e., depth, total path length (average depth), and number of nodes. We have created tools based on extensions of dynamic programming to study totally optimal trees. These tools are applicable to both exact and approximate decision trees, and allow us to make multi-stage optimization of decision trees relative to different parameters and to count the number of optimal trees. Based on the experimental results we have formulated the following hypotheses (and subsequently proved): for almost all Boolean functions there exist totally optimal decision trees (i) relative to the depth and number of nodes, and (ii) relative to the depth and average depth.

  11. 'Total disability' and the wrongness of killing.

    Science.gov (United States)

    Omelianchuk, Adam

    2015-08-01

    Walter Sinnott-Armstrong and Franklin G Miller recently argued that the wrongness of killing is best explained by the harm that comes to the victim, and that 'total disability' best explains the nature of this harm. Hence, killing patients who are already totally disabled is not wrong. I maintain that their notion of total disability is ambiguous and that they beg the question with respect to whether there are abilities left over that remain relevant for the goods of personhood and human worth. If these goods remain, then something more is lost in death than in 'total disability,' and their explanation of what makes killing wrong comes up short. But if total disability is equivalent with death, then their argument is an interesting one.

  12. Single-Incision Laparoscopic Total Colectomy

    Science.gov (United States)

    Ojo, Oluwatosin J.; Carne, David; Guyton, Daniel

    2012-01-01

    Background and Objectives: To present our experience with a single-incision laparoscopic total colectomy, along with a literature review of all published cases on single-incision laparoscopic total colectomy. Methods: A total of 22 cases were published between 2010 and 2011, with our patient being case 23. These procedures were performed in the United States and United Kingdom. Surgical procedures included total colectomy with end ileostomy, proctocolectomy with ileorectal anastomosis, and total proctocolectomy with ileopouch-anal anastomosis. Intraoperative and postoperative data are analyzed. Results: Twenty-two of the 23 cases were performed for benign cases including Crohns, ulcerative colitis, and familial adenomatous polyposis. One case was performed for adenocarcinoma of the cecum. The mean age was 35.3 years (range, 13 to 64), the mean body mass index was 20.1 (range, 19 to 25), mean operative time was 175.9 minutes (range, 139 to 216), mean blood loss was 95.3mL (range, 59 to 200), mean incision length was 2.61cm (range, 2 to 3). Average follow-up was 4.6 months with 2 reported complications. Conclusions: Single-incision laparoscopic total colectomy is feasible and safe in the hands of an experienced surgeon. It has been performed for both benign and malignant cases. It is comparable to the conventional multi-port laparoscopic total colectomy. PMID:22906326

  13. 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.

  14. Dislocation following revision total hip arthroplasty.

    Science.gov (United States)

    Gioe, Terence J

    2002-04-01

    Dislocation is a relatively common complication following revision total hip arthroplasty. Risk factors include surgical approach, gender, underlying diagnosis, comorbidities, surgical experience, and previous surgery; for later dislocations, risk factors include wear/deformation of polyethylene, trauma, and decreased muscle strength. Prevention and precaution are the watchwords for dislocations following revision total hip arthroplasty. For dislocations that do occur, treatment rests first on identifying the source of instability. Most dislocations can be managed by closed reduction. Constrained components may increase success rates, but only for appropriate indications. Prevention and treatment of dislocations following revision total hip arthroplasty are discussed in this article.

  15. 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 $b_t(G_{n,4})$.

  16. Total solar eclipse of 1995 October 24

    Science.gov (United States)

    Espenak, Fred; Anderson, Jay

    1994-01-01

    A total eclipse of the sun will be visible from Asia and the Pacific Ocean on 24 Oct. 1995. The path of the moon's shadow begins in the Middle East and sweeps across India, Southeast Asia, and the waters of the Indonesian archipelago before ending at sunset in the Pacific. Detailed predictions for this event are presented and include besselian elements, geographic coordinates of the path of totality, physical ephemeris of the umbra, topocentric limb profile corrections, local circumstances for 400 cities, maps of the eclipse path, weather prospects, the lunar limb profile, and the sky during totality.

  17. 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.

  18. 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.

  19. Total Solar Eclipse--A Caribbean Adventure.

    Science.gov (United States)

    Green, Steven; Tunstall, Louisa; Tunstall, Neil

    1999-01-01

    Describes the experiences of two high school students who traveled to the Caribbean island of Curacao to view a total solar eclipse and prepare methods for teaching classmates about the eclipse the following school year. (Author/WRM)

  20. 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...

  1. Practical considerations for permanent total enclosures

    Energy Technology Data Exchange (ETDEWEB)

    Worrall, M. [Amcec Adsorption Systems, Schaumburg, IL (United States)

    1997-12-31

    This paper considers some of the practical consideration of Permanent Total Enclosures (PTEs) for gravure printing facilities. In particular the dispersion of fugitive losses from the presses by thermal air currents generated by heat from the press dryers.

  2. 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.

  3. A Convergent Total Synthesis of Methoxatin

    NARCIS (Netherlands)

    Hendrickson, James B.; Vries, Johannes G. de

    1982-01-01

    We report a convergent total synthesis of the coenzyme methoxatin (1) by linking a pyrrole subunit with an uvitonic acid derivative and oxidative photocyclization to a deoxymethoxatin triester, followed by seven refunctionalization steps to 1.

  4. 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...

  5. 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...

  6. 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...

  7. 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...

  8. 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...

  9. Total Quality Management: A Selected Bibliography

    Science.gov (United States)

    1993-03-01

    Quality Institute. INTRODUCTION TO TOTAL QUALITY MANAGEMENT IN THE FEDERAL GOVERNMENT, by Frank L. Lewis and others. Washington: May 1991. 34pp...1993, pp. 26-29. Schermerhorn , Michele. "High-Performance Work Teams: Another Management Fad?" QUALITY DIGEST, Vol. 11, October 1991, pp. 37-52...58pp. (TS156 H59 1991) US Office of Personnel Management . Federal Quality Institute. INTRODUCTION TO TOTAL QUALITY MANAGEMENT IN THE FEDERAL

  10. Photoproduction total cross section and shower development

    CERN Document Server

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

    2015-01-01

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

  11. [Treatment of infected total hip endoprostheses].

    Science.gov (United States)

    Zilkens, K W; Forst, R; Casser, H R

    1989-07-01

    In total hip arthroplasty the most serious complication besides aseptic loosening is infection. The results observed in 42 cases of infected hip arthroplasties are presented. In contrast to early superficial infection, deep infection following total hip replacement is difficult to treat. Depending on the general condition of the patient, a well-defined, adequate treatment is required. In patients at vital risk the provocation of a permanent fistula can be recommended as an alternative method in preference to revision arthroplasty.

  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. Regio and stereoselectivity in ionic cycloadditions

    Indian Academy of Sciences (India)

    Venkatachalam Tamilmani; Durairajan Senthilnathan; Ponnambalam Venuvanalingam

    2008-03-01

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

  14. Totally semi-continuous and semi totally-continuous functions in double fuzzy topological spaces

    Science.gov (United States)

    Mahmood Mohammed, Fatimah; Md Noorani, Mohd Salmi; Salleh, Abdul Razak

    2013-04-01

    The aim of this paper is to introduce new classes of functions called totally-continuous functions and its variants totally semi-continuous functions and semi totally-continuous functions in double fuzzy topological spaces. Their characterizations, examples and relationship with other notions of continuous functions in this space are provided.

  15. Total lymphoid irradiation of intractable rheumatoid arthritis

    Energy Technology Data Exchange (ETDEWEB)

    Herbst, M.; Fritz, H.; Sauer, R.

    1986-12-01

    Eleven patients with intractable rheumatoid arthritis were treated with fractionated total lymphoid irradiation, (total dose 20 Gy). Lasting improvement in clinical symptoms was found in four patients during treatment and the remaining patients experienced similar benefit within 2 months of irradiation. There was marked reduction in exacerbations and number of joints involved. Morning stiffness, joint swelling and tenderness decreased. Complications included severe fatigue during treatment and acute bacterial arthritis in multiple joints in one patient. Four patients have since died, one of renal failure, another of cardiogenic shock following surgery 3 and 24 months after total lymphoid irradiation. Both had generalised amyloidosis. The third patient developed joint empyema and died of toxic cardiac failure. The fourth died 3 months after resection of a Kaposi's sarcoma complicated by wound infection which responded to treatment. Immunologically, total lymphoid irradiation resulted in suppression of the absolute lymphocyte count and reduction in T-helper cells, the number of T-suppressor cells remaining unchanged. These data provide evidence of T-cell involvement in the pathogenesis of rheumatoid arthritis. Total lymphoid irradiation can induce sustained improvement in clinical disease activity, but severe, possibly fatal, side-effects cannot be ignored.

  16. Totally implantable catheter embolism: two related cases

    Directory of Open Access Journals (Sweden)

    Rodrigo Chaves Ribeiro

    Full Text Available CONTEXT AND OBJECTIVE: Long-term totally implantable catheters (e.g. Port-a-Cath® are frequently used for long-term venous access in children with cancer. The use of this type of catheter is associated with complications such as infection, extrusion, extravasation and thrombosis. Embolism of catheter fragments is a rare complication, but has potential for morbidity. The aim here was to report on two cases in which embolism of fragments of a long-term totally implantable catheter occurred. DESIGN AND SETTING: Case series study at Hospital do Servidor Público Estadual, São Paulo. METHODS: Retrospective review of catheter embolism in oncological pediatric patients with long-term totally implantable catheters. RESULTS: The first patient was a 3-year-old girl diagnosed with stage IV Wilms' tumor. Treatment was started with the introduction of a totally implantable catheter through the subclavian vein. At the time of removal, it was realized that the catheter had fractured inside the heart. An endovascular procedure was necessary to remove the fragment. The second case was a boy diagnosed with stage II Wilms' tumor at the age of two years. At the time of removal, it was noticed that the catheter had disconnected from the reservoir and an endovascular procedure was also necessary to remove the embolized catheter. CONCLUSION: Embolism of fragments of totally implantable catheters is a rare complication that needs to be recognized even in asymptomatic patients.

  17. 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.

  18. Heterotopic bone formation following total shoulder arthroplasty

    DEFF Research Database (Denmark)

    Kjaersgaard-Andersen, P.; Frich, Lars Henrik; Sjøbjerg, J.O.

    1989-01-01

    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...... 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...... 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....

  19. Total Solar Eclipse of 2008 August 01

    Science.gov (United States)

    Espenak, F.; Anderson, J.

    2007-01-01

    On 2008 August 01, a total eclipse of the Sun is visible from within a narrow corridor that traverses half the Earth. The path of the Moon's umbral shadow begins in northern Canada and extends across Greenland, the Arctic, central Russia, Mongolia, and China. A partial eclipse is seen within the much broader path of the Moon's penumbral shadow, which includes northeastern North America, most of Europe and Asia. Detailed predictions for this event are presented and include besselian elements, geographic coordinates of the path of totality, physical ephemeris of the umbra, topocentric limb profile corrections, local circumstances for 308 cities, maps of the eclipse path, weather prospects, the lunar limb profile and the sky during totality. Information on safe eclipse viewing and eclipse photography is included.

  20. Total Solar Eclipse of 2006 March 29

    Science.gov (United States)

    Espenak, F.; Anderson, J.

    2004-01-01

    On 2006 March 29, a total eclipse of the Sun will be visible from within a narrow corridor which traverses half the Earth. The path of the Moon's umbral shadow begins in Brazil and extends across the Atlantic, northern Africa, and central Asia where it ends at sunset in western Mongolia. A partial eclipse will be seen within the much broader path of the Moon's penumbral shadow, which includes the northern two thirds of Africa, Europe, and central Asia.Detailed predictions for this event are presented and include besselian elements, geographic coordinates of the path of totality, physical ephemeris of the umbra, topocentric limb profile corrections, local circumstances for approximately 350 cities, maps of the eclipse path, weather prospects, the lunar limb profile, and the sky during totality. Information on safe eclipse viewing and eclipse photography is included.

  1. 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...

  2. Noise measurement in total knee arthroplasty

    Directory of Open Access Journals (Sweden)

    Lukas A Holzer

    2014-01-01

    Full Text Available Few studies have been performed to analyze noise levels produced by various surgical instruments in the operating room (OR. The highest levels of noise that have been described were due to instruments used for total knee arthroplasty (TKA. These high levels of noise might be a potential health hazard for patients and medical staff. Therefore, we aimed to measure noise levels of current instruments that are widely used worldwide. During a conventional primary TKA the levels of noise in the OR were measured using a Class 1 integrating-averaging sound level meter. The highest A-weighted equivalent level was produced when using a hammer during the implantation of the femoral and tibial components with 90.2 dBA. In total surgical instruments were used for about 10% of the total time of surgery. Noise exposure due to instrument use during TKA does not seem to be a potential health hazard for medical staff or patients.

  3. 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.

  4. 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.

  5. Total Solar Eclipse of 1997 March 9

    Science.gov (United States)

    Espenak, Fred; Anderson, Jay

    1995-01-01

    A total eclipse of the Sun will be visible from Asia and the Pacific Ocean on 1997 March 9. The path of the Moon's umbral shadow begins in eastern Kazakhstan and travels through Mongolia and eastern Siberia, where it swings northward to end at sunset in the Arctic Ocean. A partial eclipse will be seen within the much broader path of the Moon's penumbral shadow, which includes eastern Asia, the northern Pacific, and the northwest corner of North America. Detailed predictions for this event are presented and include besselian elements, geographic coordinates of the path of totality, physical ephemeris of the umbra, topocentric limb profile corrections, local circumstances for 280 cities, maps of the eclipse path, weather prospects, the lunar limb profile, and the sky during totality. Tips and suggestions are also given on how to safely view and photograph the eclipse.

  6. Total Solar Eclipse of 2001 June 21

    Science.gov (United States)

    Espenak, Fred; Anderson, Jay

    1999-01-01

    On 2001 June 21, a total eclipse of the Sun will be visible from within a narrow corridor which traverses the Southern Hemisphere. The path of the Moon's umbral shadow begins in the South Atlantic, crosses southern Africa and Madagascar, and ends at sunset in the Indian Ocean. A partial eclipse will be seen within the much broader path of the Moon's penumbral shadow, which includes eastern South America and the southern two thirds of Africa. Detailed predictions for this event are presented and include besselian elements, geographic coordinates of the path of totality, physical ephemeris of the umbra, topocentric limb profile corrections, local circumstances for approximately 350 cities, maps of the eclipse path, weather prospects, the lunar limb profile and the sky during totality. Tips and suggestions are also given on how to safely view and photograph the eclipse.

  7. Total Solar Eclipse of 2002 December 04

    Science.gov (United States)

    Espenak, Fred; Anderson, Jay

    2001-01-01

    On 2002 December 04, a total eclipse of the Sun will be visible from within a narrow corridor which traverses the Southern Hemisphere. The path of the Moon's umbral shadow begins in the South Atlantic, crosses southern Africa and the Indian Ocean, and ends at sunset in southern Australia. A partial eclipse will be seen within the much broader path of the Moon's penumbral shadow, which includes the southern two thirds of Africa, Antarctica, Indian Ocean and Australia. Detailed predictions for this event are presented and include besselian elements, geographic coordinates of the path of totality, physical ephemeris of the umbra, topocentric limb profile corrections, local circumstances for approximately 400 cities, maps of the eclipse path, weather prospects, the lunar limb profile and the sky during totality. Information on safe eclipse viewing and eclipse photography is included.

  8. Total Solar Eclipse of 1999 August 11

    Science.gov (United States)

    Espenak, Fred; Anderson, Jay

    1997-01-01

    On 1999 August 11, a total eclipse of the Sun will be visible from within a narrow corridor which traverses the Eastern Hemisphere. The path of the Moon's umbral shadow begins in the Atlantic and crosses central Europe, the Middle East, and India, where it ends at sunset in the Bay of Bengal. A partial eclipse will be seen within the much broader path of the Moon's penumbral shadow, which includes northeastern North America, all of Europe, northern Africa, and the western half of Asia. Detailed predictions for this event are presented and include besselian elements, geographic coordinates of the path of totality, physical ephemeris of the umbra, topocentric limb profile corrections, local circumstances for approximately 1400 cities, maps of the eclipse path, weather prospects, the lunar limb profile, and the sky during totality. Tips and suggestions are also given on how to safely view and photograph the eclipse.

  9. Total internal reflection ellipsometry: principles and applications.

    Science.gov (United States)

    Arwin, Hans; Poksinski, Michal; Johansen, Knut

    2004-05-20

    A concept for a measurement technique based on ellipsometry in conditions of total internal reflection is presented. When combined with surface plasmon resonance (SPR) effects, this technique becomes powerful for monitoring and analyzing adsorption and desorption on thin semitransparent metal films as well as for analyzing the semitransparent films themselves. We call this technique total internal reflection ellipsometry (TIRE). The theory of ellipsometry under total internal reflection combined with SPR is discussed for some simple cases. For more advanced cases and to prove the concept, simulations are performed with the Fresnel formalism. The use of TIRE is exemplified by applications in protein adsorption, corrosion monitoring, and adsorption from opaque liquids on metal surfaces. Simulations and experiments show greatly enhanced thin-film sensitivity compared with ordinary ellipsometry.

  10. Chambolle's Projection Algorithm for Total Variation Denoising

    Directory of Open Access Journals (Sweden)

    Joan Duran

    2013-12-01

    Full Text Available Denoising is the problem of removing the inherent noise from an image. The standard noise model is additive white Gaussian noise, where the observed image f is related to the underlying true image u by the degradation model f=u+n, and n is supposed to be at each pixel independently and identically distributed as a zero-mean Gaussian random variable. Since this is an ill-posed problem, Rudin, Osher and Fatemi introduced the total variation as a regularizing term. It has proved to be quite efficient for regularizing images without smoothing the boundaries of the objects. This paper focuses on the simple description of the theory and on the implementation of Chambolle's projection algorithm for minimizing the total variation of a grayscale image. Furthermore, we adapt the algorithm to the vectorial total variation for color images. The implementation is described in detail and its parameters are analyzed and varied to come up with a reliable implementation.

  11. Correlations between corneal and total wavefront aberrations

    Science.gov (United States)

    Mrochen, Michael; Jankov, Mirko; Bueeler, Michael; Seiler, Theo

    2002-06-01

    Purpose: Corneal topography data expressed as corneal aberrations are frequently used to report corneal laser surgery results. However, the optical image quality at the retina depends on all optical elements of the eye such as the human lens. Thus, the aim of this study was to investigate the correlations between the corneal and total wavefront aberrations and to discuss the importance of corneal aberrations for representing corneal laser surgery results. Methods: Thirty three eyes of 22 myopic subjects were measured with a corneal topography system and a Tschernig-type wavefront analyzer after the pupils were dilated to at least 6 mm in diameter. All measurements were centered with respect to the line of sight. Corneal and total wavefront aberrations were calculated up to the 6th Zernike order in the same reference plane. Results: Statistically significant correlations (p corneal and total wavefront aberrations were found for the astigmatism (C3,C5) and all 3rd Zernike order coefficients such as coma (C7,C8). No statistically significant correlations were found for all 4th to 6th order Zernike coefficients except for the 5th order horizontal coma C18 (p equals 0.003). On average, all Zernike coefficients for the corneal aberrations were found to be larger compared to Zernike coefficients for the total wavefront aberrations. Conclusions: Corneal aberrations are only of limited use for representing the optical quality of the human eye after corneal laser surgery. This is due to the lack of correlation between corneal and total wavefront aberrations in most of the higher order aberrations. Besides this, the data present in this study yield towards an aberration balancing between corneal aberrations and the optical elements within the eye that reduces the aberration from the cornea by a certain degree. Consequently, ideal customized ablations have to take both, corneal and total wavefront aberrations, into consideration.

  12. An Operational Perspective of Total Lightning Information

    Science.gov (United States)

    Nadler, David J.; Darden, Christopher B.; Stano, Geoffrey; Buechler, Dennis E.

    2009-01-01

    The close and productive collaborations between the NWS Warning and Forecast Office, the Short Term Prediction and Research Transition Center at NASA Marshall Space Flight Center and the University of Alabama in Huntsville have provided a unique opportunity for science sharing and technology transfer. One significant technology transfer that has provided immediate benefits to NWS forecast and warning operations is the use of data from the North Alabama Lightning Mapping Array. This network consists of ten VHF receivers deployed across northern Alabama and a base station located at the National Space Science and Technology Center. Preliminary investigations done at WFO Huntsville, along with other similar total lightning networks across the country, have shown distinct correlations between the time rate-of-change of total lightning and trends in intensity/severity of the parent convective cell. Since May 2003 when WFO HUN began receiving these data - in conjunction with other more traditional remotely sensed data (radar, satellite, and surface observations) -- have improved the situational awareness of the WFO staff. The use of total lightning information, either from current ground based systems or future space borne instrumentation, may substantially contribute to the NWS mission, by enhancing severe weather warning and decision-making processes. Operational use of the data has been maximized at WFO Huntsville through a process that includes forecaster training, product implementation, and post event analysis and assessments. Since receiving these data, over 50 surveys have been completed highlighting the use of total lightning information during significant events across the Tennessee Valley. In addition, around 150 specific cases of interest have been archived for collaborative post storm analysis. From these datasets, detailed trending information from radar and total lightning can be compared to corresponding damage reports. This presentation will emphasize

  13. 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.

  14. Modelling total energy costs of sports centres

    Energy Technology Data Exchange (ETDEWEB)

    Boussabaine, A.H.; Kirkham, R.J.; Grew, R.J. [Liverpool Univ., School of Architecture and Building Engineering, Liverpool (United Kingdom)

    1999-12-07

    Providing and maintaining safe and comfortable conditions in sport centres raises many issues, particularly cost. The paper gives an overview of the factors associated with sport centre servicing and attempts to highlight the governing factors associated with this, particularly energy costs. A total of 19 sport centres in the City of Liverpool in the UK are investigated, using data elicited from the Liverpool Leisure Services Directorate. The energy operating costs were analysed using statistical methods. Six models were developed to predict total energy costs. Testing and validation results showed a high level of model accuracy. The models would be of use to professionals involved in feasibility studies at the design stage. (Author)

  15. Measuring Total and Germinable Spore Populations

    Science.gov (United States)

    Noell, A.C.; Yung, P.T.; Yang, W.; Lee, C.; Ponce, A.

    2011-01-01

    It has been shown that bacterial endospores can be enumerated using a microscopy based assay that images the luminescent halos from terbium ions bound to dipicolinic acid, a spore specific chemical marker released upon spore germination. Further development of the instrument has simplified it towards automation while at the same time improving image quality. Enumeration of total spore populations has also been developed allowing measurement of the percentage of viable spores in any population by comparing the germinable/culturable spores to the total. Percentage viability will allow a more quantitative comparison of the ability of spores to survive across a wide range of extreme environments.

  16. Activation energies of pericyclic reactions: performance of DFT, MP2, and CBS-QB3 methods for the prediction of activation barriers and reaction energetics of 1,3-dipolar cycloadditions, and revised activation enthalpies for a standard set of hydrocarbon pericyclic reactions.

    Science.gov (United States)

    Ess, Daniel H; Houk, K N

    2005-10-27

    Activation barriers and reaction energetics for the three main classes of 1,3-dipolar cycloadditions, including nine different reactions, were evaluated with the MPW1K and B3LYP density functional methods, MP2, and the multicomponent CBS-QB3 method. The CBS-QB3 values were used as standards for 1,3-dipolar cycloaddition activation barriers and reaction energetics, and the density functional theory (DFT) and MP2 methods were benchmarked against these values. The MPW1K/6-31G* method and basis set performs best for activation barriers, with a mean absolute deviation (MAD) value of 1.1 kcal/mol. The B3LYP/6-31G* method and basis set performs best for reaction enthalpies, with a MAD value of 2.4 kcal/mol, while the MPW1K method shows large errors for reaction energetics. The MP2 method gives the expected systematic underestimation of barriers. Concerted and nearly synchronous transition structures are predicted by all DFT and MP2 methods. Also reported are revised estimated 0 K experimental activation enthalpies for a standard set of hydrocarbon pericyclic reactions and updated comparisons to experiment for DFT, ab initio, and multicomponent methods. B3LYP and MPW1K methods with MAD values of 1.5 and 2.1 kcal/mol, respectively, fortuitously outperform the multicomponent CBS-QB3 method, which has a MAD value of 2.3. The MAD value of the O3LYP functional improves to 2.4 kcal/mol from the previously reported 3.0 kcal/mol.

  17. 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...

  18. 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

  19. The Leica TCRA1105 Reflectorless Total Station

    Energy Technology Data Exchange (ETDEWEB)

    Gaudreault, F.

    2005-09-06

    This poster provides an overview of SLAC's TCRA1105 reflectorless total station for the Alignment Engineering Group. This instrument has shown itself to be very useful for planning new construction and providing quick measurements to difficult to reach or inaccessible surfaces.

  20. Recurrent hemarthrosis after total knee arthroplasty.

    Science.gov (United States)

    Rukavina, Alexander; Kerkhoffs, Gino M M J; Schneider, Philipp; Kuster, Markus S

    2010-07-01

    This report describes a case of spontaneous recurrent hemarthrosis of the knee that presented 4 weeks after total knee arthroplasty. Femoral arteriography showed a false aneurysm of a branch of the inferior lateral geniculate artery. Therapeutic embolization of the arterial branch was performed using three platinum coils with good clinical result and good knee joint function. Hemarthrosis has not recurred since embolization.

  1. Recurrent hemarthrosis after total knee arthroplasty

    OpenAIRE

    Rukavina, A.; Kerkhoffs, G. M. M. J.; Schneider, P.; Kuster, M S

    2010-01-01

    This report describes a case of spontaneous recurrent hemarthrosis of the knee that presented 4 weeks after total knee arthroplasty. Femoral arteriography showed a false aneurysm of a branch of the inferior lateral geniculate artery. Therapeutic embolization of the arterial branch was performed using three platinum coils with good clinical result and good knee joint function. Hemarthrosis has not recurred since embolization.

  2. Recurrent hemarthrosis after total knee arthroplasty

    NARCIS (Netherlands)

    Rukavina, A.; Kerkhoffs, G.M.M.J.; Schneider, P.; Kuster, M.S.

    2010-01-01

    This report describes a case of spontaneous recurrent hemarthrosis of the knee that presented 4 weeks after total knee arthroplasty. Femoral arteriography showed a false aneurysm of a branch of the inferior lateral geniculate artery. Therapeutic embolization of the arterial branch was performed usin

  3. SOFT TISSUE BALANCING IN TOTAL HIP ARTHROPLASTY.

    Directory of Open Access Journals (Sweden)

    Pencho Kosev

    2015-03-01

    Full Text Available We present our experience with the soft tissue balancing in total hip arthroplasty. Detailed indications, planning and surgical technique are presented. The described procedures are performed on 278 hips for a period of 6 years (2008-2014. We conclude that the outcome of a THA can be improved by balancing the stability, ROM, muscle strength and limb length equality.

  4. 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

  5. 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.

  6. 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…

  7. Total Quality Management Goes to Community College.

    Science.gov (United States)

    DeCosmo, Richard D.; And Others

    1991-01-01

    This article details the four-year implementation of Total Quality Management at Delaware County Community College (Pennsylvania) to conserve resources, improve effectiveness, assure quality, and increase participation in decision making. Reported are planning, execution, and monitoring activities of the Implementation Team; specific problems…

  8. 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

  9. 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

  10. 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…

  11. The Total Solar Eclipse, March 1970

    Science.gov (United States)

    Glenn, William H.

    1970-01-01

    Describes the circumstances of the total and partial solar eclipse of March 7, 1970 in certain American cities. Also discussed are (1) a classroom demonstration of the cause of solar eclipses, (2) techniques for safely observing the eclipse, and (3) what to observe during the eclipse. Bibliography. (LC)

  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. Transanal total mesorectal excision - a systematic review

    DEFF Research Database (Denmark)

    Bjørn, Maya Xania; Perdawood, Sharaf Karim

    2015-01-01

    of the dissection. We aimed to evaluate the literature on TaTME. METHODS: We performed a systematic search of the literature in the PubMed and Embase databases. Both authors assessed the studies. All publications on TaTME were included with the exception of review articles. RESULTS: A total of 29 studies (336...

  14. 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

  15. 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...

  16. 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.

  17. 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.

  18. Mineral Analysis of Whole Grain Total Cereal

    Science.gov (United States)

    Hooker, Paul

    2005-01-01

    The quantitative analysis of elemental iron in Whole Grain Total Cereal using visible spectroscopy is suitable for a general chemistry course for science or nonscience majors. The more extensive mineral analysis, specifically for the elements iron, calcium and zinc, is suitable for an instrumental or quantitative analysis chemistry course.

  19. Tikhonov Regularization and Total Least Squares

    DEFF Research Database (Denmark)

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

    2000-01-01

    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...

  20. 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…

  1. 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)

  2. 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.

  3. 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.

  4. Extracorporeal total artificial heart as bailout surgery.

    Science.gov (United States)

    Perrodin, Stéphanie F; Muller, Olivier; Gronchi, Fabrizio; Liaudet, Lucas; Hullin, Roger; Kirsch, Matthias

    2017-03-01

    We report the use of a total extracorporeal heart for uncontrolled bleeding following a proximal left anterior descending artery perforation, using two centrifugal ventricular assist devices after heart explantation. The literature describing similar techniques and patient outcomes for this "bailout" technique are reviewed.

  5. 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

  6. 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

  7. 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 …

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  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. A modified total synthesis of cystothiazole A

    Institute of Scientific and Technical Information of China (English)

    BAI YueXia; BAO JiLai; REN Jun; WANG ZhongWen

    2009-01-01

    A modified total synthesis of cystothiazole A is described.In this synthetic strategy,a one-step transformation of acylated oxazolidinone to β-ketoester has been successfully applied,thus making the synthetic route more efficient.This method may also be potentially applied in synthesis of other related β-substituted-β-methoxyl acrylates (bb-MOAs).

  14. Total N, total P and organic matters content in floodplain soils of Xianghai Nature Reserve

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Soil sediment samples of 10 layers with a spacing of 10 cm each were collected in different floodplain zones adjacent to Huolin River in the Xianghai Nature Reserve, and contents of total N, total P and organic matters were analyzed. The results showed that contents of total N, total P and organic matters were generally decreasing with the increase of distance from sample locations to the river channel, and contents of the three items were generally higher in the upper soil layer than that in the lower soil layer. The content variations displayed how flooding functions influenced nutrient matter content variations in floodplain soils since the flood inundation frequencies of the sample locations varied. The correlation analysis displayed that there were remarkable relativities between total N, total P and organic matters within definite spatial distance from the Huolin River channel.

  15. Total Limb Rotation after Unilateral Total Knee Arthroplasty: Side-to-Side Discrepancy.

    Science.gov (United States)

    Oh, Kwang-Jun; Yoon, Seok-Tae; Ko, Young-Bong

    2016-08-01

    Total limb rotation, an important anatomical feature of the lower limb, is defined as any rotation of the lower limb on its longitudinal axis. The aim of the present study was to evaluate the discrepancies of rotational profiles of total limb between nonoperated and operated limb following unilateral total knee arthroplasty. We conducted an analysis of the computed tomography (CT) data from 32 patients undergoing primary unilateral total knee arthroplasty. Using these CT scan, rotational profiles of total limb, such as femoral neck anteversion angle expressed as femoral torsion angle (FTA), tibial torsion angle (TTA), knee joint rotation angle (KJRA), and total limb rotation (TLR) were measured. There were significant discrepancies of FTA and KJRA between operated and nonoperated limb following unilateral total knee arthroplasty. The mean difference of operated and nonoperated side for FTA and KJRA were -6.51 ± 11.88 degrees (p = 0.0041) and -6.83 ± 5.04 degrees (p knee joint can lead to a total limb rotational discrepancy in patient undergoing unilateral total knee arthroplasty.

  16. 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. ...

  17. 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.

  18. Increasing productivity through Total Reuse Management (TRM)

    Science.gov (United States)

    Schuler, M. P.

    1991-01-01

    Total Reuse Management (TRM) is a new concept currently being promoted by the NASA Langley Software Engineering and Ada Lab (SEAL). It uses concepts similar to those promoted in Total Quality Management (TQM). Both technical and management personnel are continually encouraged to think in terms of reuse. Reuse is not something that is aimed for after a product is completed, but rather it is built into the product from inception through development. Lowering software development costs, reducing risk, and increasing code reliability are the more prominent goals of TRM. Procedures and methods used to adopt and apply TRM are described. Reuse is frequently thought of as only being applicable to code. However, reuse can apply to all products and all phases of the software life cycle. These products include management and quality assurance plans, designs, and testing procedures. Specific examples of successfully reused products are given and future goals are discussed.

  19. Total variation projection with first order schemes.

    Science.gov (United States)

    Fadili, Jalal M; Peyre, Gabriel

    2011-03-01

    This article proposes a new algorithm to compute the projection on the set of images whose total variation is bounded by a constant. The projection is computed through a dual formulation that is solved by first order non-smooth optimization methods. This yields an iterative algorithm that applies iterative soft thresholding to the dual vector field, and for which we establish convergence rate on the primal iterates. This projection algorithm can then be used as a building block in a variety of applications such as solving inverse problems under a total variation constraint, or for texture synthesis. Numerical results are reported to illustrate the usefulness and potential applicability of our TV projection algorithm on various examples including denoising, texture synthesis, inpainting, deconvolution and tomography problems. We also show that our projection algorithm competes favorably with state-of-the-art TV projection methods in terms of convergence speed.

  20. Generalized principles of unchanging total concentration.

    Science.gov (United States)

    Kottke, Peter A; Fedorov, Andrei G

    2005-09-08

    We consider the transport of multiple reacting species under the continuum assumption in situations such as those that frequently arise in electroanalytical chemistry. Under certain limitations, it has been shown that the total species concentration (as defined by Oldham and Feldberg) of such a system is uniform and constant. In this work, we extend the limits of the previous analysis to enable greater applicability. This is accomplished by using either of two new dependent variables, which are generalizations of the concept of total concentration. Then, conditions are determined under which the dependent variable will be uniform and constant in time. From a practical viewpoint, the described formalism allows one to simplify the multispecies transport problem formulation by eliminating one equation from the system of governing equations.

  1. 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.

  2. Total ankle replacement. Design evolution and results.

    Science.gov (United States)

    van den Heuvel, Alexander; Van Bouwel, Saskia; Dereymaeker, Greta

    2010-04-01

    The ankle joint has unique anatomical, biomechanical and cartilaginous structural characteristics that allow the joint to withstand the very high mechanical stresses and strains over years. Any minor changes to any of these features predispose the joint to osteoarthritis. Total ankle replacement (TAR) is evolving as an alternative to ankle arthrodesis for the treatment of end-stage ankle osteoarthritis. Initial implant designs from the early 1970s had unacceptably high failure and complication rates. As a result many orthopaedic surgeons have restricted the use of TAR in favour of ankle arthrodesis. Long term follow-up studies following ankle arthrodesis show risks of developing adjacent joint osteoarthritis. Therefore research towards a successful ankle replacement continues. Newer designs and longer-term outcome studies have renewed the interest in ankle joint replacement. We present an overview of the evolution, results and current concepts of total ankle replacement.

  3. 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

  4. Total positive curvature of circular DNA

    DEFF Research Database (Denmark)

    Bohr, Jakob; Olsen, Kasper Wibeck

    2013-01-01

    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...... 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......The properties of double-stranded DNA and other chiral molecules depend on the local geometry, i.e., on curvature and torsion, yet the paths of closed chain molecules are globally restricted by topology. When both of these characteristics are to be incorporated in the description of circular chain...

  5. 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.

  6. 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.

  7. 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.)

  8. Total Quality Management (TQM): Group Dynamics Workshop

    Science.gov (United States)

    1990-05-15

    Improvement: A Process for Innovation and Consensus, Prentice Hall, 1990. Tuckman , Bruce , W., "Development Sequence in Small Groups," Psychological Bulletin...four stages. (Source: Tuckman , 1955) " How long it will take any specific TQM group to move through these stages can vary widely. It can happen in as...using the HEAR Model : H = Hear E = Empathize A = Analyze R= Respond. Total Quality Management * Active listening improves group productivity in several

  9. Calidad total: fuente de ventaja competitiva

    OpenAIRE

    Tarí Guilló, Juan José

    2000-01-01

    El objeto de este trabajo es analizar la dirección de la calidad estudiando sus pilares básicos como son, la planificación, organización y control por un lado y los aspectos humanos por otro, centrándonos en sus dos elementos clave para desarrollar la calidad total: el liderazgo y la involucración de todos los empleados.

  10. 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

  11. The total parenteral nutrition service: an update.

    OpenAIRE

    1988-01-01

    A total parenteral nutrition (TPN) service was established in Oxford in 1978 and the results of the first 3 years were published in 1983. Since then the service has provided intravenous nutritional support to an increasing number of patients, representing a considerable and increasing financial burden on the constrained hospital budget. To assess whether this expansion is justified, and whether regular review has improved the care given to patients, a further audit has been performed for the ...

  12. 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.)

  13. Dilemmas in Uncemented Total Hip Arthroplasty

    OpenAIRE

    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, Biomet) was evaluated. In conclusion, at an average follow-up of 8 years, this proximally HA-coated femoral component showed favorable clinical and radiological outcome and excellent survivorship. In ...

  14. Total synthesis of mangiferin, homomangiferin, and neomangiferin.

    Science.gov (United States)

    Wei, Xiong; Liang, Danlin; Wang, Qing; Meng, Xiangbao; Li, Zhongjun

    2016-09-21

    Total synthesis of mangiferin, homomangiferin, and neomangiferin, three C-glycosyl xanthone natural products with a wide spectrum of pharmacological effects, has been achieved starting from 2,3,4,6-tetra-O-benzyl-α/β-d-glucopyranose. The key steps involve a stereoselective Lewis acid promoted C-glycosylation of protected phloroglucinol with tetrabenzylglucopyranosyl acetate and a highly regioselective base-induced cyclization for the construction of the core xanthone skeleton.

  15. Current concepts in total femoral replacement

    OpenAIRE

    Ramanathan, Deepak; Siqueira, Marcelo BP; Klika, Alison K.; Higuera, Carlos A.; Barsoum, Wael K.; Joyce, Michael J

    2015-01-01

    Total femoral replacement (TFR) is a salvage arthroplasty procedure used as an alternative to lower limb amputation. Since its initial description in the mid-20th century, this procedure has been used in a variety of oncologic and non-oncologic indications. The most compelling advantage of TFR is the achievement of immediate fixation which permits early mobilization. It is anticipated that TFR will be increasingly performed as the rate of revision arthroplasty rises worldwide. The existing li...

  16. 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.

  17. 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.

  18. 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...

  19. Total Spinal Block after Thoracic Paravertebral Block.

    Science.gov (United States)

    Beyaz, Serbülent Gökhan; Özocak, Hande; Ergönenç, Tolga; Erdem, Ali Fuat; Palabıyık, Onur

    2014-02-01

    Thoracic paravertebral block (TPVB) can be performed with or without general anaesthesia for various surgical procedures. TPVB is a popular anaesthetic technique due to its low side effect profile and high analgesic potency. We used 20 mL of 0.5% levobupivacaine for a single injection of unilateral TPVB at the T7 level with neurostimulator in a 63 year old patient with co-morbid disease who underwent cholecystectomy. Following the application patient lost consciousness, and was intubated. Haemodynamic instability was normalised with rapid volume replacement and vasopressors. Anaesthetic drugs were stopped at the end of the surgery and muscle relaxant was antagonised. Return of mucle strenght was shown with neuromuscular block monitoring. Approximately three hours after TPVB, spontaneous breathing started and consciousness returned. A total spinal block is a rare and life-threatening complication. A total spinal block is a complication of spinal anaesthesia, and it can also occur after peripheral blocks. Clinical presentation is characterised by hypotension, bradicardia, apnea, and cardiac arrest. An early diagnosis and appropriate treatment is life saving. In this case report, we want to present total spinal block after TPVB.

  20. MAJOR HEPATIC RESECTION UNDER TOTAL VASCULAR EXCLUSION

    Institute of Scientific and Technical Information of China (English)

    季加孚; 顾晋; 苏向前; 焦春雨; 王怡; 欧阳晓辉; 董培德; 杨成旺

    2001-01-01

    Objective: To eveluate major liver resections with vascular exclusion (TVE) in patients with hepatocellular carcinoma (HCC). Methods: Sixteen consecutive, major liver resections performed with TVE in HCC patients were analyzed retrospectively. The patients' mean ages were 54 years. Ten patients had cirrhosis and eleven patients had chronic hepatitis B. Results: There was no perioperative death and the mean hospital stay was 20 days and the average amount of intraoperative blood transfusion was 400 mL (range 0-2000 mL). Forty-four percent of the patients did not receive intraoperative blood transfusion. The mean total bilirubin(T-BIL) and aspartate aminotransferase (AST) were 24μmol/L (range 8-56μmol/L) and 56 IU/L (range 10-204 IU/L) measured prior to discharge. Conclusion: In our experience, total vascular exclusion is invaluable in major or difficult liver resections, especially when lesions adjacent to the hepatic veins and vena cava. It is associated with a low blood transfusion requirement and a low incidence of complications. It further obviates the need for dissection of the porta hepatis thus reduces the associated risks. Total vascular exclusion time of 30min appears to be well tolerated, even in patients with cirrhosis..

  1. 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.

  2. Climate Change and Tropical Total Lightning

    Science.gov (United States)

    Albrecht, R.; Petersen, W.; Buechler, D.; Goodman, S.; Blakeslee, R.; Christian, H.

    2009-01-01

    While global warming is regarded as a fact by many in the scientific community, its future impact remains a challenge to be determined and measured. The International Panel on Climate Change (IPCC) assessment report (IPCC, 2007) shows inconclusive answers on global rainfall trends and general agreement on a future drier climate with increased global warming. The relationship between temperature, humidity and convection is not linear and is strongly dependent on regional scale features, such as topography and land cover. Furthermore, the relationship between convective lightning production (thunderstorms) and temperature is even more complicated, being subjected to the cloud dynamics and microphysics. Total lightning (intracloud and cloud-to-ground) monitoring is a relatively new field of observation. Global and tropical total lightning began to be more extensively measured by satellites in the mid 90s. In this scope, the Lightning Imaging Sensor (LIS) onboard of the Tropical Rainfall Measurement Mission (TRMM) has been operational for over 11 years. Here we address total lightning trends observed by LIS from 1998 to 2008 in different temporal (annual and seasonal) and spatial (large and regional) scales. The observed 11-year trends are then associate to different predicted/hypothesized climate change scenarios.

  3. Improved selection in totally monotone arrays

    Energy Technology Data Exchange (ETDEWEB)

    Mansour, Y. (Harvard Univ., Cambridge, MA (United States). Aiken Computation Lab.); Park, J.K. (Sandia National Labs., Albuquerque, NM (United States)); Schieber, B. (International Business Machines Corp., Yorktown Heights, NY (United States). Thomas J. Watson Research Center); Sen, S. (AT and T Bell Labs., Murray Hill, NJ (United States))

    1991-01-01

    This paper's main result is an O(({radical}{bar m}lgm)(n lg n) + mlg n)-time algorithm for computing the kth smallest entry in each row of an m {times} n totally monotone array. (A two-dimensional A = a(i,j) is totally monotone if for all i{sub 1} < i{sub 2} and j{sub 1} < j{sup 2}, < a(i{sub 1},j{sub 2}) implies a(i{sub 2},j{sub 1})). For large values of k (in particular, for k=(n/2)), this algorithm is significantly faster than the O(k(m+n))-time algorithm for the same problem due to Kravets and Park. An immediate consequence of this result is an O(n{sup 3/2} lg{sup 2}n)-time algorithm for computing the kth nearest neighbor of each vertex of a convex n-gon. In addition to the main result, we also give an O(n lg m)-time algorithm for computing an approximate median in each row of an m {times} n totally monotone array; this approximate median is an entry whose rank in its row lies between (n/4) and (3n/4) {minus} 1. 20 refs., 3 figs.

  4. 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.

  5. 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

  6. Total quality control - TQC : controle total de qualidade na area de serviços

    OpenAIRE

    Reque Calisaya, Ramiro Benjamin

    2010-01-01

    Trata-se de uma análise teórica sobre os conceitos modernos de comtrole de qualidade - CQ, refletidos no TOTAL QUALITY CONTROL - TQC - Controle Total de Qualidade, aplicados às áreas de serviços das empresas industriais e às empresas fornecedoras de serviços

  7. Revision total elbow arthroplasty with the linked Coonrad-Morrey total elbow arthroplasty

    DEFF Research Database (Denmark)

    Plaschke, Hans Christian; Thillemann, Theis; Belling-Sørensen, Anne Kathrine;

    2013-01-01

    In this retrospective study we evaluated the short- to medium-term results after 20 Coonrad-Morrey revision total elbow arthroplasties (TEAs).......In this retrospective study we evaluated the short- to medium-term results after 20 Coonrad-Morrey revision total elbow arthroplasties (TEAs)....

  8. 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.

  9. Drain tip culture following total knee arthroplasty

    Directory of Open Access Journals (Sweden)

    Bahubali Aski

    2015-02-01

    Full Text Available Background: Placing a suction drain following total knee replacement is usual practice which is been followed by many surgeons. Closed suction drainage following arthroplasty is a routine with the aim of preventing wound hematoma and thereby reducing the risk of infection. Surgical site infections in orthopaedic surgeries are disastrous and often lead to significant morbidity and mortality. Usefulness of drain tip culture in predicting the wound infection is been tested but results are controversial. Methods: It is a prospective study of 546 drains (352 patients who underwent unilateral or bilateral Total Knee Arthroplasty (TKA. The drain tip was sent for culture at the time of removing. Cultures from the SSI (surgical site infection were also collected. Cases that had at least six months of follow up were included in the study. However in one patient with superficial infection, the drain tip culture was negative. Results: Drain tip culture was positive in total of 18 patients. Three patients had developed deep infection and 10 patients had superficial infection. All three patients with deep infection and 9 out of 10 patients of superficial infection were culture positive. Out of 8 culture positive superficial infections, one had different bacteria identified from the site. Drain tip culture was positive in 3.39% of drains and infection rate was positive in 1.88% of wounds. On statistical analysis we found drain tip culture sensitivity of 90%, specificity of 98.46%, positive predictive value of 52.9% and negative predictive value of 99.8%. Conclusion: Drain tip culture positivity helps in predicting the future chance of developing the infection. If drain tip culture is negative, then there is almost near nil chances of infection. [Int J Res Med Sci 2015; 3(2.000: 409-411

  10. 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.

  11. 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.

  12. 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

  13. TOTAL QUALITY MANAGEMENT AND CONTEMPORARY HOTEL INDUSTRY

    Directory of Open Access Journals (Sweden)

    Ivica Batinić

    2013-04-01

    Full Text Available Strong competition in the market has caused the development of a new management approach known as Total Quality Management (TQM. Due to importance that quality plays in achieving competitive advantage, the hotel industry started to apply TQM. During the introduction of these systems, hotel companies may use different approaches to suit their own buseiness requirements. In doing so, 'TQM standards' can be used, or various international standards and models of business excellence Malcolm Balridge National Quality Award and European Quality Award.

  14. Periprosthetic osteolysis after total wrist arthroplasty

    DEFF Research Database (Denmark)

    Boeckstyns, Michel E H; Herzberg, Guillaume

    2014-01-01

    Background and Literature Review Periprosthetic osteolysis (PPO) after second- or third-generation total wrist arthroplasty (TWA), with or without evident loosening of the implant components, has previously been reported in the literature, but rarely in a systematic way. Purpose The purpose....... Conclusion Periprosthetic loosening is frequent following a TWA. In our series it was not necessarily associated with implant loosening and seemed to stabilize within 3 years. Close and continued observation is, however, recommended. Level of Evidence Therapeutic IV....

  15. On the total variation dictionary model.

    Science.gov (United States)

    Zeng, Tieyong; Ng, Michael K

    2010-03-01

    The goal of this paper is to provide a theoretical study of a total variation (TV) dictionary model. Based on the properties of convex analysis and bounded variation functions, the existence of solutions of the TV dictionary model is proved. We then show that the dual form of the model can be given by the minimization of the sum of the l(1) -norm of the dual solution and the Bregman distance between the curvature of the primal solution and the subdifferential of TV norm of the dual solution. This theoretical result suggests that the dictionary must represent sparsely the curvatures of solution image in order to obtain a better denoising performance.

  16. 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...... incorporates our prior information about the solution and thus compensates for the loss of accuracy in the data. A consequence is that smaller data acquisition times can be used, thus reducing a patients exposure to X-rays in medical scanning and speeding up non-destructive measurements in materials science....

  17. 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.

  18. 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...

  19. 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.

  20. Totally nonnegative Grassmannian and Grassmann polytopes

    CERN Document Server

    Lam, Thomas

    2015-01-01

    These are lecture notes intended to supplement my second lecture at the Current Developments in Mathematics conference in 2014. In the first half of article, we give an introduction to the totally nonnegative Grassmannian together with a survey of some more recent work. In the second half of the article, we give a definition of a Grassmann polytope motivated by work of physicists on the amplituhedron. We propose to use Schubert calculus and canonical bases to replace linear algebra and convexity in the theory of polytopes.

  1. 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.

  2. Total Synthesis of (-)-Salvinorin A.

    Science.gov (United States)

    Line, Nathan J; Burns, Aaron C; Butler, Sean C; Casbohm, Jerry; Forsyth, Craig J

    2016-12-12

    Salvinorin A (1) is natural hallucinogen that binds the human κ-opioid receptor. A total synthesis has been developed that parlays the stereochemistry of l-(+)-tartaric acid into that of (-)-1 via an unprecedented allylic dithiane intramolecular Diels-Alder reaction to obtain the trans-decalin scaffold. Tsuji allylation set the C9 quaternary center and a late-stage stereoselective chiral ligand-assisted addition of a 3-titanium furan upon a C12 aldehyde/C17 methyl ester established the furanyl lactone moiety. The tartrate diol was finally converted into the C1,C2 keto-acetate.

  3. 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

  4. 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.

  5. 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.

  6. Total hip arthroplasty after previous fracture surgery.

    Science.gov (United States)

    Krause, Peter C; Braud, Jared L; Whatley, John M

    2015-04-01

    Total hip arthroplasty can be a very effective salvage treatment for both failed fracture surgery and hip arthritis that may occur after prior fracture surgery. The rate of complications is significantly increased including especially infection, dislocation, and loosening. Complications are more likely to occur after failed open reduction and internal fixation than after posttraumatic arthritis. Adequately ruling out infection before hip arthroplasty can be difficult. The best predictor of infection is a prior infection. Long-term outcomes can be comparable to outcomes in other conditions if complications are avoided.

  7. 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.

  8. 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.

  9. Lower Limb Ischaemia Complicating Total Hip Arthroplasty

    Directory of Open Access Journals (Sweden)

    Shiu-Wai Chan

    2012-06-01

    Full Text Available This article is about two patients having vascular injuries complicating total hip arthroplasty because of intraoperative indirect injuries. One patient had a delayed presentation of acute lower limb ischaemia, in which he required amputation of his left second toe because of ischaemic gangrene. The other patient had acute lower limb ischaemia leading to permanent muscle and nerve damage because of delayed recognition. Both patients had vascular interventions for the indirect vascular injuries. Preoperative workup for suspicious underlying peripheral vascular disease, intraoperative precautions, and perioperative period of vascular status monitoring are essential for prevention and early detection of such sinister events.

  10. Renal function after elective total hip replacement

    DEFF Research Database (Denmark)

    Perregaard, Helene; Damholt, Mette B; Solgaard, Søren

    2016-01-01

    Background and purpose - Acute kidney injury (AKI) is associated with increased short-term and long-term mortality in intensive care populations and in several surgical specialties, but there are very few data concerning orthopedic populations. We have studied the incidence of AKI and the prevale......Background and purpose - Acute kidney injury (AKI) is associated with increased short-term and long-term mortality in intensive care populations and in several surgical specialties, but there are very few data concerning orthopedic populations. We have studied the incidence of AKI...... involving all primary elective total hip replacements performed from January 2003 through December 2012. Patient demographics and creatinine values were registered. We evaluated the presence of CKD and AKI according to the international guidelines for kidney disease (KDIGO Acute Kidney Injury Workgroup 2013...... reduced kidney function, was seen in 374 individuals (11%). Interpretation - Development of acute kidney injury appears to be a substantial problem compared to other complications related to elective total hip arthroplasty, i.e. luxation and infection. Patients with pre-existing chronic kidney disease may...

  11. 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.

  12. 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.

  13. Imaging of total colonic Hirschsprung disease

    Energy Technology Data Exchange (ETDEWEB)

    Stranzinger, Enno; DiPietro, Michael A.; Strouse, Peter J. [University of Michigan Health System, Section of Pediatric Radiology, Ann Arbor, MI (United States); Teitelbaum, Daniel H. [University of Michigan Health System, Section of Pediatric Surgery, Ann Arbor, MI (United States)

    2008-11-15

    Hirschsprung disease (HD) is a functional obstruction of the bowel caused by the absence of intrinsic enteric ganglion cells. The diagnosis of total colonic HD (TCHD) based on contrast enemas is difficult in newborns because radiological findings vary. To evaluate the radiographic and contrast enema findings in patients with pathologically proven TCHD. From 1966 to 2007, 17 records from a total of 31 patients with TCHD were retrospectively evaluated for diameter and shape of the colon, diameter of the small bowel, bowel wall contour, ileal reflux, abdominal calcifications, pneumoperitoneum, filling defects, transitional zones and rectosigmoid index. Three colonic patterns of TCHD were found: microcolon, question-mark-shape colon and normal caliber colon. Additional findings included spasmodic colon, ileal reflux, delayed evacuation and abdominal calcifications. Colonic transitional zones were found in eight patients with TCHD. The diagnosis of TCHD is difficult to establish by contrast enema studies. The length of the aganglionic small bowel and the age of the patient can influence the radiological findings in TCHD. The transitional zone and the rectosigmoid index can be false-positive in TCHD. The colon can appear normal. Consider TCHD if the contrast enema study is normal but the patient remains symptomatic and other causes of distal bowel obstruction have been excluded. (orig.)

  14. Annular and Total Solar Eclipses of 2010

    Science.gov (United States)

    Espenak, Fred; Anderson, J.

    2008-01-01

    While most NASA eclipse bulletins cover a single eclipse, this publication presents predictions for two solar eclipses during 2010. This has required a different organization of the material into the following sections. Section 1 -- Eclipse Predictions: The section consists of a general discussion about the eclipse path maps, Besselian elements, shadow contacts, eclipse path tables, local circumstances tables, and the lunar limb profile. Section 2 -- Annular Solar Eclipse of 2010 Ja n 15: The section covers predictions and weather prospects for the annular eclipse. Section 3 -- Total Solar Eclipse of 2010 Jul 11: The se ction covers predictions and weather prospects for the total eclipse. Section 4 -- Observing Eclipses: The section provides information on eye safety, solar filters, eclipse photography, and making contact timings from the path limits. Section 5 -- Eclipse Resources: The final section contains a number of resources including information on the IAU Working Group on Eclipses, the Solar Eclipse Mailing List, the NASA eclipse bulletins on the Internet, Web sites for the two 2010 eclipses, and a summary identifying the algorithms, ephemerides, and paramete rs used in the eclipse predictions.

  15. Reduction Methods for Total Reaction Cross Sections

    Science.gov (United States)

    Gomes, P. R. S.; Mendes Junior, D. R.; Canto, L. F.; Lubian, J.; de Faria, P. N.

    2016-03-01

    The most frequently used methods to reduce fusion and total reaction excitation functions were investigated in a very recent paper Canto et al. (Phys Rev C 92:014626, 2015). These methods are widely used to eliminate the influence of masses and charges in comparisons of cross sections for weakly bound and tightly bound systems. This study reached two main conclusions. The first is that the fusion function method is the most successful procedure to reduce fusion cross sections. Applying this method to theoretical cross sections of single channel calculations, one obtains a system independent curve (the fusion function), that can be used as a benchmark to fusion data. The second conclusion was that none of the reduction methods available in the literature is able to provide a universal curve for total reaction cross sections. The reduced single channel cross sections keep a strong dependence of the atomic and mass numbers of the collision partners, except for systems in the same mass range. In the present work we pursue this problem further, applying the reduction methods to systems within a limited mass range. We show that, under these circumstances, the reduction of reaction data may be very useful.

  16. Total body irradiation for children with malignancies

    Energy Technology Data Exchange (ETDEWEB)

    Sanuki, Eiichi; Maeno, Toshio; Kamata, Rikisaburo; Tanaka, Yoshiaki; Mugishima, Hideo [Nihon Univ., Tokyo (Japan). School of Medicine

    1995-12-01

    Total body irradiation combined with high dose chemotherapy has been performed just before bone marrow transplantation in 35 children with advanced malignancies, with the object of achieving successful transplantation and improving the prognosis. Simulation was performed as follows: back scatter, flatness, dose accumulation using randophantom and dose distribution using a thermo-luminescence dosimeter and linac-graphy. The standard error of dose distribution was within 10%. In neuroblastoma, of which there were 14 cases in stage IV and one case in stage III, the 5-year survival rate was 55%. In leukemia, of which all cases were in the high-risk group (7 cases of acute lymphoblastic leukemia and 2 of acute myeloblastic leukemia) the 5-year survival rate was 55%. The 5 cases having first remission survived disease-free while the 4 cases having non-first remission died. In malignant lymphoma (6 cases in stage IV and one case in stage III, with bulky mass) the 5-year survival rate was 67%. Four cases with other diagnoses (severe aplastic anemia, and others) all survived. As yet no side effects resulting from total body irradiation have been recognized in our cases, but a longer follow-up period is necessary to observe possible late side effects. (author).

  17. Lubrication regimes in lumbar total disc arthroplasty.

    Science.gov (United States)

    Shaheen, A; Shepherd, D E T

    2007-08-01

    A number of total disc arthroplasty devices have been developed. Some concern has been expressed that wear may be a potential failure mode for these devices, as has been seen with hip arthroplasty. The aim of this paper was to investigate the lubrication regimes that occur in lumbar total disc arthroplasty devices. The disc arthroplasty was modelled as a ball-and-socket joint. Elastohydrodynamic lubrication theory was used to calculate the minimum film thickness of the fluid between the bearing surfaces. The lubrication regime was then determined for different material combinations, size of implant, and trunk velocity. Disc arthroplasties with a metal-polymer or metal-metal material combination operate with a boundary lubrication regime. A ceramic-ceramic material combination has the potential to operate with fluid-film lubrication. Disc arthroplasties with a metal-polymer or metal-metal material combination are likely to generate wear debris. In future, it is worth considering a ceramic-ceramic material combination as this is likely to reduce wear.

  18. Previous gastric bypass surgery complicating total thyroidectomy.

    Science.gov (United States)

    Alfonso, Bianca; Jacobson, Adam S; Alon, Eran E; Via, Michael A

    2015-03-01

    Hypocalcemia is a well-known complication of total thyroidectomy. Patients who have previously undergone gastric bypass surgery may be at increased risk of hypocalcemia due to gastrointestinal malabsorption, secondary hyperparathyroidism, and an underlying vitamin D deficiency. We present the case of a 58-year-old woman who underwent a total thyroidectomy for the follicular variant of papillary thyroid carcinoma. Her history included Roux-en-Y gastric bypass surgery. Following the thyroid surgery, she developed postoperative hypocalcemia that required large doses of oral calcium carbonate (7.5 g/day), oral calcitriol (up to 4 μg/day), intravenous calcium gluconate (2.0 g/day), calcium citrate (2.0 g/day), and ergocalciferol (50,000 IU/day). Her serum calcium levels remained normal on this regimen after hospital discharge despite persistent hypoparathyroidism. Bariatric surgery patients who undergo thyroid surgery require aggressive supplementation to maintain normal serum calcium levels. Preoperative supplementation with calcium and vitamin D is strongly recommended.

  19. 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.

  20. Extensor mechanism allograft in total knee arthroplasty

    Science.gov (United States)

    Helito, Camilo Partezani; Gobbi, Riccardo Gomes; Tozi, Mateus Ramos; Félix, Alessandro Monterroso; Angelini, Fábio Janson; Pécora, José Ricardo

    2013-01-01

    Objective To analyze the experience with allograft transplantation of the extensor mechanism in total knee arthroplasty and compare results with the international experience. Methods We retrospectively evaluated three cases of extensor mechanism allograft after total knee arthroplasty performed in our hospital with the aid of one of the few tissue banks in Brazil and attempt to establish whether our experiences were similar to others reported in the world literature regarding patient indication, techniques, and outcomes. Results Two cases went well with the adopted procedure, and one case showed bad results and progressed to amputation. As shown in the literature, the adequate tension of the graft, appropriate tibial fixation and especially the adequate patient selection are the better predictors of good outcomes. Previous chronic infection can be an unfavorable predictor. Conclusion This surgical procedure has precise indication, albeit uncommon, either because of the rarity of the problem or because of the low availability of allografts, due to the scarcity of tissue banks in Brazil. Level of Evidence IV, Case Series. PMID:24453688