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Sample records for absolute asymmetric synthesis

  1. Competitive Exclusion Principle in Ecology and Absolute Asymmetric Synthesis in Chemistry.

    PubMed

    Ribó, Josep M; Hochberg, David

    2015-10-01

    The key concepts underlying the Frank model (1953) for spontaneous asymmetric synthesis in chemistry are traced back to the pioneering works of Volterra (1926) and Lotka (1932) on biological species competition. The Lotka-Volterra (L-V) two-species exclusive competition model reduces to the Frank model for the special case of distinguishable but degenerate species (i.e., the enantiomers). The important ecological principle of competitive exclusion, originally derived from the L-V two-competitors model, is a consequence of sufficiently antagonistic interactions between the species competing for limited common resources, or mutual inhibition, as the term is known in the chemical literature on absolute asymmetric synthesis. The L-V and Frank models are described by the same general differential equations, nevertheless a crucial thermodynamic distinction between these models is necessary to correlate ecological selection and chemical selectivity arising from 1) the absence of reversibility in biological transformations, in marked contrast to chemical reactions, and 2) the constraints in chemical scenarios on the reaction rate constants required to fulfill the principle of micro-reversibility. Chirality 27:722-727, 2015. © 2015 Wiley Periodicals, Inc. PMID:26301597

  2. Stochastic and empirical models of the absolute asymmetric synthesis by the Soai-autocatalysis.

    PubMed

    Barabás, Béla; Zucchi, Claudia; Maioli, Marco; Micskei, Károly; Pályi, Gyula

    2015-02-01

    Absolute asymmetric synthesis (AAS) is the preparation of pure (or excess of one) enantiomer of a chiral compound from achiral precursor(s) by a chemical reaction, without enantiopure chiral additive and/or without applied asymmetric physical field. Only one well-characterized example of AAS is known today: the Soai-autocatalysis. In an attempt at clarification of the mechanism of this particular reaction we have undertaken empirical and stochastic analysis of several parallel AAS experiments. Our results show that the initial steps of the reaction might be controlled by simple normal distribution ("coin tossing") formalism. Advanced stages of the reaction, however, appear to be of a more complicated nature. Symmetric beta distribution formalism could not be brought into correspondence with the experimental observations. A bimodal beta distribution algorithm provided suitable agreement with the experimental data. The parameters of this bimodal beta function were determined by a Pólya-urn experiment (simulated by computer). Interestingly, parameters of the resulting bimodal beta function give a golden section ratio. These results show, that in this highly interesting autocatalysis two or even perhaps three catalytic cycles are cooperating. An attempt at constructing a "designed" Soai-type reaction system has also been made. PMID:25644371

  3. Asymmetric Synthesis and Absolute Configuration Assignment of a New Type of Bedaquiline Analogue.

    PubMed

    Qiao, Chang-Jiang; Wang, Xiao-Kui; Xie, Fei; Zhong, Wu; Li, Song

    2015-01-01

    Bedaquiline is the first FDA-approved new chemical entity to fight multidrug-resistant tuberculosis in the last forty years. Our group replaced the quinoline ring with a naphthalene ring, leading to a new type of triarylbutanol skeleton. An asymmetric synthetic route was established for our bedaquiline analogues, and the goal of assigning their absolute configurations was achieved by comparison of experimental and calculated electronic circular dichroism spectra, and was confirmed by the combined use of circular dichroism and NMR spectroscopy. PMID:26690407

  4. On the Traces of Absolute Enantioselective Synthesis

    NASA Astrophysics Data System (ADS)

    Barabás, Béla; Caglioti, Luciano; Faglioni, Francesco; Florini, Nicola; Lazzeretti, Paolo; Maioli, Marco; Micskei, Károly; Rábai, Gyula; Taddei, Ferdinando; Zucchi, Claudia; Pályi, Gyula

    2007-12-01

    The main goal of this communication is to show the utility of empirical approaches combined with mathematical methods in the research regarding the molecular basis of biological chirality. Preparative results (enantiomeric excesses, e.e.) obtained in asymmetric autocatalysis with (AAC) and without (AES) chiral additive were analyzed. Statistical calculations show, that AES (absolute enantioselective synthesis) experiments yield two independent groups of results with prevalence of the R- or S-enantiomer. These are distributed asymmetrically in a second-order beta distribution. Empirical calculations both on AAC and EAS enable to identify the very low (statistical) e.e.-s amplified by AES. These initial e.e.-s show normal distribution. Possible molecular-level reasons of these results were controlled by quantum chemical MO calculations and compatible mechanism(s) are discussed.

  5. Asymmetric total synthesis of (+)-dragmacidin D reveals unexpected stereocomplexity.

    PubMed

    Zhang, Fengying; Wang, Bin; Prasad, Pritesh; Capon, Robert J; Jia, Yanxing

    2015-03-20

    The first asymmetric total synthesis of the bis-indole marine alkaloid (+)-dragmacidin D (1) has been achieved. This synthesis revises an earlier configurational assignment based on biosynthetic considerations and assigns an R absolute configuration to (+)-1. The current studies reveal that natural dragmacidin D is isolated as either a racemate or a scalemic mixture (39% ee). PMID:25730523

  6. Synthesis and absolute configuration of hormone alpha1.

    PubMed

    Yajima, Arata; Qin, Yong; Zhou, Xuan; Kawanishi, Naoki; Xiao, Xue; Wang, Jue; Zhang, Dan; Wu, Yi; Nukada, Tomoo; Yabuta, Goro; Qi, Jianhua; Asano, Tomoyo; Sakagami, Youji

    2008-04-01

    An important biological event in phytopathogens of the genus Phytophthora is sexual reproduction, which is conducted by two mating types, A1 and A2. A factor known as hormone alpha1 is secreted by the A1 mating type and induces the formation of sexual spores (oospores) in the A2 mating type. Here we describe the asymmetric synthesis and assignment of the absolute configuration of hormone alpha1 by oospore-inducing assays of the synthesized isomers. PMID:18297064

  7. Photochirogenesis: Photochemical models on the absolute asymmetric formation of amino acids in interstellar space

    NASA Astrophysics Data System (ADS)

    Meinert, Cornelia; de Marcellus, Pierre; Le Sergeant D'Hendecourt, Louis; Nahon, Laurent; Jones, Nykola C.; Hoffmann, Søren V.; Bredehöft, Jan Hendrik; Meierhenrich, Uwe J.

    2011-10-01

    Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b) the occurrence of L-enantiomer-enriched amino acids in carbonaceous meteorites, and c) the observation of CPL of the same helicity over large distance scales in the massive star-forming region of Orion. These topics are of high importance in topical biophysical research and will be discussed in this review. Further evidence that amino acids and other molecules of prebiotic interest are asymmetrically formed in space comes from studies on the enantioselective photolysis of amino acids by UV-CPL. Also, experiments have been performed on the absolute asymmetric photochemical synthesis of enantiomer-enriched amino acids from mixtures of astrophysically relevant achiral precursor molecules using UV-circularly polarized photons. Both approaches are based on circular dichroic transitions of amino acids that will be highlighted here as well. These results have strong implications on our current understanding of how life's precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids.

  8. Total synthesis and absolute configuration of malyngamide W.

    PubMed

    Qi, Xian-Liang; Zhang, Jun-Tao; Feng, Jian-Peng; Cao, Xiao-Ping

    2011-05-21

    A concise enantioselective synthesis of malyngamide W (1) and its 2'-epimer was described. The strategy was based on three key steps: (1) ozonolysis of compound 11 which was derived from (R)-(-)-carvone 8, followed by copper-iron-catalyzed rearrangement to give the key cyclohex-2-enone intermediate 5, (2) Nozaki-Hiyama-Kishi coupling reaction between aldehyde 4 and iodide 14 to afford alcohol 3, and (3) asymmetric (R)-CBS reduction of the ketone functionality in compound 21 to establish the C-2' chiral center in the target compound 1. The absolute configuration of malyngamide W (1) was thus confirmed via the synthesis of 1 and 2'-epi-1. PMID:21445440

  9. Quantifying Absolute Protein Synthesis Rates Reveals Principles Underlying

    E-print Network

    Zhang, Jianzhi

    Quantifying Absolute Protein Synthesis Rates Reveals Principles Underlying Allocation of Cellular present a genome-wide approach, based on ribosome profiling, for measuring absolute protein synthesis- lyses of protein synthesis. INTRODUCTION Protein biosynthesis is by far the largest consumer of energy

  10. Asymmetric synthesis of tertiary thiols and thioethers

    PubMed Central

    MacLellan, Paul

    2011-01-01

    Summary Enantiomerically pure tertiary thiols provide a major synthetic challenge, and despite the importance of chiral sulfur-containing compounds in biological and medicinal chemistry, surprisingly few effective methods are suitable for the asymmetric synthesis of tertiary thiols. This review details the most practical of the methods available. PMID:21647256

  11. Studies Culminating in the Total Synthesis and Determination of the Absolute Configuration of (-)-Saudin

    PubMed Central

    Boeckman, Robert K.; del Rosario Ferreira, Maria Rico; Mitchell, Lorna H.; Shao, Pengcheng; Neeb, Michael J.; Fang, Yue

    2011-01-01

    A full account of studies that culminated in the total synthesis of both antipodes and the assignment of its absolute configuration of Saudin, a hypoglycemic natural product. Two approaches are described, the first proceeding though bicyclic lactone intermediates and related second monocyclic esters. The former was obtained via asymmetric Diels-Alder cycloaddition and the latter by an asymmetric annulation protocol. Both approaches employ a Lewis acid promoted Claisen rearrangement, with the successful approach taking advantage of bidentate chelation to control the facial selectivity of the key Claisen rearrangement PMID:22523435

  12. Asymmetric catalysis in organic synthesis

    SciTech Connect

    Reilly, S.D.; Click, D.R.; Grumbine, S.K.; Scott, B.L.; Watkins, J.G.

    1998-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal of the project was to prepare new catalyst systems, which would perform chemical reactions in an enantioselective manner so as to produce only one of the possible optical isomers of the product molecule. The authors have investigated the use of lanthanide metals bearing both diolate and Schiff-base ligands as catalysts for the enantioselective reduction of prochiral ketones to secondary alcohols. The ligands were prepared from cheap, readily available starting materials, and their synthesis was performed in a ''modular'' manner such that tailoring of specific groups within the ligand could be carried out without repeating the entire synthetic procedure. In addition, they have developed a new ligand system for Group IV and lanthanide-based olefin polymerization catalysts. The ligand system is easily prepared from readily available starting materials and offers the opportunity to rapidly prepare a wide range of closely related ligands that differ only in their substitution patterns at an aromatic ring. When attached to a metal center, the ligand system has the potential to carry out polymerization reactions in a stereocontrolled manner.

  13. A novel and practical asymmetric synthesis of dapoxetine hydrochloride

    PubMed Central

    Zhu, Yijun; Liu, Zhenren; Li, Hongyan

    2015-01-01

    Summary A novel and practical asymmetric synthesis of dapoxetine hydrochloride by using the chiral auxiliary (S)-tert-butanesulfinamide was explored. The synthesis was concise, mild, and easy to perform. The overall yield and stereoselectivity were excellent.

  14. Highly Efficient Asymmetric Synthesis of -Amino Acid Derivatives via

    E-print Network

    Zhang, Xumu

    Highly Efficient Asymmetric Synthesis of -Amino Acid Derivatives via Rhodium pure -amino acids and their deriva- tives are important building blocks for the synthesis of -peptides of -amino acids has attracted extensive interest. Although several stoichio- metric and catalytic methods

  15. Catalytic asymmetric formal synthesis of beraprost

    PubMed Central

    Kobayashi, Yusuke; Kuramoto, Ryuta

    2015-01-01

    Summary The first catalytic asymmetric synthesis of the key intermediate for beraprost has been achieved through an enantioselective intramolecular oxa-Michael reaction of an ?,?-unsaturated amide mediated by a newly developed benzothiadiazine catalyst. The Weinreb amide moiety and bromo substituent of the Michael adduct were utilized for the C–C bond formations to construct the scaffold. All four contiguous stereocenters of the tricyclic core were controlled via Rh-catalyzed stereoselective C–H insertion and the subsequent reduction from the convex face.

  16. Microscale Synthesis of Chiral Alcohols via Asymmetric Catalytic Transfer Hydrogenation

    ERIC Educational Resources Information Center

    Peeters, Christine M.; Deliever, Rik; De Vos, Dirk

    2009-01-01

    Synthesis of pure enantiomers is a key issue in industry, especially in areas connected to life sciences. Catalytic asymmetric synthesis has emerged as a powerful and practical tool. Here we describe an experiment on racemic reduction and asymmetric reduction via a catalytic hydrogen transfer process. Acetophenone and substituted acetophenones are…

  17. Synthesis and Determination of Absolute Configuration of Lentztrehalose A.

    PubMed

    Zhang, Ming; Wada, Shun-Ichi; Amemiya, Fuyuki; Watanabe, Takumi; Shibasaki, Masakatsu

    2015-01-01

    The synthesis of lentztrehalose A, a naturally occurring trehalose derivative exhibiting various biological activities including autophagy-inducing activity, was achieved. The synthesis commenced with the selective protection of hydroxyl groups of commercially available trehalose, followed by the introduction of the side chain moiety by two methods: 1) prenylation and successive diastereoselective dihydroxylation; or 2) etherification by opening of the chiral epoxide. The present synthetic study clarified the unreported absolute configuration of the secondary alcohol part in the side chain portion. PMID:26521862

  18. Asymmetric Total Synthesis of the Epoxykinamycin FL-120B’**

    PubMed Central

    Scully, Stephen S.; Porco, John A.

    2012-01-01

    Turn up the heat: An asymmetric total synthesis of the epoxykinamycin FL-120B’ is reported. The synthesis establishes a route to epoxide-containing diazobenzofluorenes which could potentially serve as monomers to the dimeric lomaiviticins. Key steps include Sharpless asymmetric epoxidation, Stille coupling, and intramolecular Friedel-Crafts acylation of atropisomeric carboxylic acids at elevated temperatures to construct the FL-120B’ core structure. PMID:21953671

  19. Group-assisted purification (GAP) chemistry for the synthesis of Velcade via asymmetric borylation of N-phosphinylimines

    PubMed Central

    Xie, Jian-bo; Luo, Jian; Winn, Timothy R; Cordes, David B

    2014-01-01

    Summary A new approach to the anticancer drug Velcade was developed by performing asymmetric borylation of an imine anchored with a chiral N-phosphinyl auxiliary. Throughout the 7-step synthesis, especially in the imine’s synthesis and in the asymmetric borylation reactions, operations and work-up were conducted in simple and easy ways without any column chromatographic purification, which defines the GAP (group-assisted purification) chemistry concept. It was found that the optically pure isomer (dr > 99:1) can be readily obtained by washing the crude mixture of the asymmetric borylation reaction with hexane; the chiral N-phosphinyl auxiliary can be easily recovered after deprotection is finished. Several other N-phosphinylimines were also investigated for the asymmetric borylation reaction. The absolute configuration of the borylation product was confirmed by single crystal X-ray diffraction analysis. PMID:24778728

  20. The asymmetric total synthesis of (+)-N-acetyl norloline.

    PubMed

    Ye, Jian-Liang; Liu, Yang; Yang, Zhi-Ping; Huang, Pei-Qiang

    2016-01-11

    The asymmetric total synthesis of (+)-N-acetyl norloline, the putative biogenic precursor of all known loline alkaloids, has been achieved in 12 steps from commercially available (R)-glyceraldehyde acetonide. The synthesis relies on the Rassu/Casiraghi's vinylogous aldol reaction, an intramolecular oxa-heteroconjugate addition and a reductive amination to establish the four contiguous stereogenic centers and construct the strained oxygen-bridge under mild conditions. PMID:26538080

  1. First asymmetric synthesis of planar chiral [2.2]metacyclophanes.

    PubMed

    Blangetti, Marco; Müller-Bunz, Helge; O'Shea, Donal F

    2013-07-14

    A general three step asymmetric synthesis of planar chiral [2.2]metacyclophanes utilizing selective benzylic and aryl metalations is described. The final enantioselective step is achieved using a (-)-sparteine mediated aryl metalation, following which electrophile reaction gives planar chiral cyclophanes with enantiomeric ratios (er) above 90?:?10. PMID:23615867

  2. Direct Catalytic Asymmetric Synthesis of ?-Hydroxy Acids from Malonic Acid.

    PubMed

    Gao, Hang; Luo, Zhenli; Ge, Pingjin; He, Junqian; Zhou, Feng; Zheng, Peipei; Jiang, Jun

    2015-12-18

    A nickel(II) catalyzed asymmetric synthesis of ?-hydroxy acids from malonic acid and ketones was developed, revealing for the first time the synthetic utility of malonic acid in the construction of chiral carboxyl acids; importantly, the synthetic potential of this strategy was further demonstrated by the rapid construction of cephalanthrin A, phaitanthrin B, cruciferane, and rice metabolites. PMID:26587748

  3. Magnetically Retrievable Catalysts for Asymmetric Synthesis

    EPA Science Inventory

    Surface modification of magnetic nanoparticles with chiral scaffolds for asymmetric catalytic applications is an elegant way of providing a special pseudo homogenous phase which could be separated using an external magnet. In this review, we summarize the use of magnetic nanopart...

  4. Asymmetric Synthesis of the Aminocyclitol Pactamycin, a Universal Translocation Inhibitor

    PubMed Central

    Sharpe, Robert J.; Malinowski, Justin T.; Johnson, Jeffrey S.

    2014-01-01

    An asymmetric total synthesis of the aminocyclopentitol pactamycin is described, which delivers the title compound in 15 steps from 2,4-pentanedione. Critical to this approach was the exploitation of a complex symmetry-breaking reduction strategy to assemble the C1, C2, and C7 relative stereochemistry within the first four steps of the synthesis. Multiple iterations of this reduction strategy are described, and a thorough analysis of stereochemical outcomes is detailed. In the final case, an asymmetric Mannich reaction was developed to install a protected amine directly at the C2 position. Symmetry-breaking reduction of this material gave way to a remarkable series of stereochemical outcomes leading to the title compound without recourse to non-strategic downstream manipulations. This synthesis is immediately accommodating to the facile preparation of structural analogs. PMID:24245656

  5. Total Synthesis, Structure Revision, and Absolute Configuration of (?)-Brevenal

    PubMed Central

    Fuwa, Haruhiko; Ebine, Makoto; Bourdelais, Andrea J.; Baden, Daniel G.; Sasaki, Makoto

    2008-01-01

    Total synthesis of structure 1 originally proposed for brevenal, a nontoxic polycyclic ether natural product isolated from the Florida red tide dinoflagellate, Karenia brevis, was accomplished. The key features of the synthesis involved (i) convergent assembly of the pentacyclic polyether skeleton based on our developed Suzuki–Miyaura coupling chemistry and (ii) stereoselective construction of the multi-substituted (E,E)-dienal side chain by using copper(I) thiophen-2-carboxylate (CuTC)-promoted modified Stille coupling. The disparity of NMR spectra between the synthetic material and the natural product required a revision of the proposed structure. Detailed spectroscopic comparison of synthetic 1 with natural brevenal, coupled with the postulated biosynthetic pathway for marine polyether natural products, suggested that the natural product was most likely represented by 2, the C26 epimer of the proposed structure 1. The revised structure was finally validated by completing the first total synthesis of (?)-2, which also unambiguously established the absolute configuration of the natural product. PMID:17177450

  6. The role of biocatalysis in the asymmetric synthesis of alkaloids

    PubMed Central

    2013-01-01

    Alkaloids are not only one of the most intensively studied classes of natural products, their wide spectrum of pharmacological activities also makes them indispensable drug ingredients in both traditional and modern medicine. Among the methods for their production, biotechnological approaches are gaining importance, and biocatalysis has emerged as an essential tool in this context. A number of chemo-enzymatic strategies for alkaloid synthesis have been developed over the years, in which the biotransformations nowadays take an increasingly ‘central’ role. This review summarises different applications of biocatalysis in the asymmetric synthesis of alkaloids and discusses how recent developments and novel enzymes render innovative and efficient chemo-enzymatic production routes possible. PMID:25580241

  7. Asymmetric Synthesis and Properties of Sulfinimines (Thiooxime S-Oxides).

    PubMed

    Davis, Franklin A.; Reddy, Rajarathnam E.; Szewczyk, Joanna M.; Reddy, G. Venkat; Portonovo, Padma S.; Zhang, Huiming; Fanelli, Dean; Thimma Reddy, R.; Zhou, Ping; Carroll, Patrick J.

    1997-04-18

    Enantiomerically pure sulfinimines (thiooxime S-oxides 10), important building blocks in the asymmetric synthesis of amine derivatives, are prepared in good to excellent yields in one step from aromatic, heteroaromatic, and aliphatic aldehydes. This protocol involves treating commercially available (R)- or (S)-menthyl p-toluenesufinate (Andersen reagent 4) with LiHMDS, followed by the aldehyde, affording (E)-10 exclusively. The sulfinimines 10 are formed via a Peterson-type olefination reaction of silylsulfinamide anion 13 with the aldehyde. Anion 13 is generated by reaction of lithium menthoxide (12a) with bis(trimethylsilyl)sulfinamide 11, which is formed in the reaction of 4 with LiHMDS. The other product formed is O-(trimethylsilyl)menthol (12c), which is isolated in >80% yield for recycling. Two other less efficient methods for the asymmetric synthesis of 10 are discussed: (i) the asymmetric oxidation of sulfenimines 6 with chiral nonracemic oxaziridines and (ii) the reaction of metal aldimines, prepared from nitriles, with 4. All of these protocols fail with ketones. PMID:11671597

  8. Allenes in catalytic asymmetric synthesis and natural product syntheses.

    PubMed

    Yu, Shichao; Ma, Shengming

    2012-03-26

    Allenes are the simplest class of cumulenes, with two contiguous C=C bonds, and show unique physical and chemical properties. These features make allenes particularly attractive in modern organic chemistry. In this Review, attention is paid to the advances made in catalytic asymmetric synthesis and natural product syntheses based on well-established reactions of allenes, such as propargylation, addition, cycloaddition, cycloisomerization, cyclization, etc., with or without catalysts. Their versatile reactivity, substituent-loading ability, axial to center chirality transfer, and controllable selectivity allow access to target molecules by unique and efficient approaches. The main topics in this Review are presented with selected examples from 2003 to 2011. PMID:22271630

  9. Mo-catalyzed asymmetric olefin metathesis in target-oriented synthesis: Enantioselective synthesis of (+)-africanol

    PubMed Central

    Weatherhead, Gabriel S.; Cortez, G. A.; Schrock, Richard R.; Hoveyda, Amir H.

    2004-01-01

    Catalytic asymmetric ring-opening metathesis (AROM) provides an efficient method for the synthesis of a variety of optically enriched small organic molecules that cannot be easily prepared by alternative methods. The development of Mo-catalyzed AROM transformations that occur in tandem with ring-closing metathesis are described. The utility of the Mo-catalyzed AROM/ring-closing metathesis is demonstrated through an enantioselective approach to the synthesis of (+)-africanol. PMID:15056762

  10. Asymmetric Synthesis of trans-2,5-Disubstituted Pyrrolidines from Enantiopure Homoallylic Amines. Synthesis of Pyrrolidine (?)-197B

    PubMed Central

    Davis, Franklin A.; Song, Minsoo; Augustine, Alexander

    2008-01-01

    Iodocyclization of sulfinimine-derived enantiopure homoallylic sulfonamides affords trans-2,5-disubstituted 3-iodopyrrolidines and represents valuable methodology for the asymmetric synthesis of this important heterocyclic ring system. PMID:16555832

  11. Absolute Configuration Determination of Azulenyl Diols Isolated From Asymmetric Pinacol Coupling.

    PubMed

    Dragu, Eugenia Andreea; Naubron, Jean-Valere; Hanganu, Anamaria; Razus, Alexandru C; Nica, Simona

    2015-11-01

    A convenient enantioselective approach for the pinacol coupling of 1-acetylazulene involving easily accessible (R)- or (S)-BINOLs as chiral additive is reported. This supposes the preformation of the chiral titanium-BINOL complex in 1:2 ratio and subsequent reduction with zinc when, 2,3-di(azulen-1-yl)butane-2,3-diol can be isolated in around 60% enantiomeric excess. The absolute configuration of the isolated enantiomers was assigned by comparison of the experimental and Boltzmann-weighted calculated VCD and ECD spectra and assigned as (+)-(2S;3S)-di(azulen-1-yl)butane-2,3-diol. Chirality 27:826-834, 2015. © 2015 Wiley Periodicals, Inc. PMID:26364568

  12. Multistep One-Pot Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

    E-print Network

    Zhao, Huimin

    as to more sustainable synthetic routes. In addition, multistep one-pot reactions can improve stereochemicalMultistep One-Pot Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis are developed are generally fine-tuned for individual reactions. In a multistep synthesis, each reaction

  13. NHC-Catalyzed Asymmetric Synthesis of Functionalized Succinimides from Enals and ?-Ketoamides

    PubMed Central

    Wang, Lei; Ni, Qijian; Blümel, Marcus; Shu, Tao; Raabe, Gerhard; Enders, Dieter

    2015-01-01

    The efficient asymmetric synthesis of highly substituted succinimides from ?,?-unsaturated aldehydes and ?-ketoamides via NHC-catalyzed [3+2] cycloaddition has been developed. The new scalable protocol significantly expands the utility of NHC catalysis for the synthesis of heterocycles and provides easy access to assemble a wide range of succinimides from simple starting materials. PMID:25877658

  14. Synthesis of asymmetric tetracarboxylic acids and corresponding dianhydrides

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2008-01-01

    This invention relates to processes for preparing asymmetrical biphenyl tetracarboxylic acids and the corresponding asymmetrical dianhydrides, namely 2,3,3',4'-biphenyl dianhydride (a-BPDA), 2,3,3',4'-benzophenone dianhydride (a-BTDA) and 3,4'-methylenediphthalic anhydride (-MDPA). By cross-coupling reactions of reactive metal substituted o-xylenes or by cross-coupling o-xylene derivatives in the presence of catalysts, this invention specifically produces asymmetrical biphenyl intermediates that are subsequently oxidized or hydrolyzed and oxidized to provide asymmetric biphenyl tetracarboxylic acids in comparatively high yields. These asymmetrical biphenyl tetracarboxylic acids are subsequently converted to the corresponding asymmetrical dianhydrides without contamination by symmetrical biphenyl dianhydrides.

  15. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines

    PubMed Central

    2013-01-01

    Summary A continuous-flow asymmetric organocatalytic photocyclization–transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Brønsted acid catalysis. The photocylization and subsequent reduction was performed with catalytic amount of chiral BINOL derived phosphoric acid diester and Hantzsch dihydropyridine as hydrogen source providing the desired products in good yields and with excellent enantioselectivities. PMID:24367413

  16. Asymmetric synthesis of syn-propargylamines and unsaturated ?-amino acids under Brønsted base catalysis

    PubMed Central

    Wang, Yingcheng; Mo, Mingjie; Zhu, Kongxi; Zheng, Chao; Zhang, Hongbin; Wang, Wei; Shao, Zhihui

    2015-01-01

    Propargylamines are important intermediates for the synthesis of polyfunctional amino derivatives and natural products and biologically active compounds. The classic method of synthesizing chiral propargylamines involves the asymmetric alkynylation of imines. Here, we report a significant advance in the catalytic asymmetric Mannich-type synthesis of propargylamines through catalytic asymmetric addition of carbon nucleophiles to C-alkynyl imines, culminating in a highly syn-selective catalytic asymmetric Mannich reaction of C-alkynyl imines that provide syn-configured propargylamines with two adjacent stereogenic centres and a transition metal-free organocatalytic asymmetric approach to ?-alkynyl-?-amino acids with high efficiency and practicality, via a chiral Brønsted base-catalysed asymmetric Mannich-type reaction of in situ generated challenging N-Boc C-alkynyl imines from previously unreported C-alkynyl N-Boc-N,O-acetals, with ?-substituted ?-keto esters and less-acidic malonate (thio)esters as nucleophiles, respectively. A catalytic activation strategy is also disclosed, which may have broad implications for use in catalysis and synthesis. PMID:26423837

  17. Asymmetric synthesis of H1 receptor antagonist (R,R)-clemastine.

    PubMed

    Lee, Sun Young; Jung, Jung Wha; Kim, Tae-Hyun; Kim, Hee-Doo

    2015-12-01

    The first asymmetric synthesis of (R,R)-clemastine (1) has been accomplished by the coupling of (R)-tertiary alcohol 2 and (R)-chloroethylpyrrolidine 3 via O-alkylation. (R)-Tertiary alcohol 2 was synthesized by stereoselective alkylation of chiral ?-benzyloxy ketone with Grignard reagent via chelation-controlled 1,4-asymmetric induction. In the reaction, chiral benzyl group acts as a chiral auxiliary as well as a protecting group. (R)-Chloroethylpyrrolidine 3 was prepared by asymmetric transformation starting with L-homoserine lactone, in which racemization-minimized N-allylation and ring-closing metathesis were involved as key steps. PMID:26219510

  18. Asymmetric total synthesis of (-)-amphidinolide V through effective combinations of catalytic transformations.

    PubMed

    Volchkov, Ivan; Lee, Daesung

    2013-04-10

    An asymmetric total synthesis of (-)-amphidinolide V was accomplished. The synthesis features a base-catalyzed alkynyl silane alcoholysis/ring-closing enyne metathesis sequence for facile construction of a 1,3-diene motif. A diene RCM followed by a ring-contractive allylic transposition of cyclic silyl ethers was incorporated for the stereoselective installation of a functionalized 1,5-diene subunit. An efficient proline-mediated direct cross-aldol condensation of two advanced aldehyde intermediates was utilized for the construction of a key ?,?-unsaturated epoxyaldehyde. This total synthesis demonstrates the prowess of metal-catalyzed transformations in complex molecule synthesis. PMID:23514007

  19. Asymmetric synthesis of N-allylic indoles via regio- and enantioselective allylation of aryl hydrazines

    PubMed Central

    Xu, Kun; Gilles, Thomas; Breit, Bernhard

    2015-01-01

    The asymmetric synthesis of N-allylic indoles is important for natural product synthesis and pharmaceutical research. The regio- and enantioselective N-allylation of indoles is a true challenge due to the favourable C3-allylation. We develop here a new strategy to the asymmetric synthesis of N-allylic indoles via rhodium-catalysed N-selective coupling of aryl hydrazines with allenes followed by Fischer indolization. The exclusive N-selectivities and good to excellent enantioselectivities are achieved applying a rhodium(I)/DTBM-Segphos or rhodium(I)/DTBM-Binap catalyst. This method permits the practical synthesis of valuable chiral N-allylated indoles, and avoids the N- or C-selectivity issue. PMID:26137886

  20. Enantioselective Synthesis of ?-Secondary and ?-Tertiary Piperazin-2-ones and Piperazines by Catalytic Asymmetric Allylic Alkylation

    PubMed Central

    Korch, Katerina M.; Eidamshaus, Christian; Behenna, Douglas C.; Nam, Sangkil; Horne, David

    2014-01-01

    The asymmetric Pd-catalyzed decarboxylative allylic alkylation of differentially N-protected piperazin-2-ones allows for the synthesis of a variety of highly enantioenriched tertiary piperazine-2-ones. Deprotection and reduction affords the corresponding tertiary piperazines, which can be employed for the synthesis of medicinally important analogs. The introduction of these chiral tertiary piperazines resulted in imatinib analogs that exhibited comparable antiproliferative activity to that of their corresponding imatinib counterparts. PMID:25382664

  1. Asymmetric Total Synthesis of Dendrobatid Alkaloids: Preparation of Indolizidine 251F and Its 3-Desmethyl

    E-print Network

    Taber, Douglass

    Asymmetric Total Synthesis of Dendrobatid Alkaloids: Preparation of Indolizidine 251F and Its 3-mail: jaube@ku.edu Abstract: Total syntheses of alkaloid 251F (1), a natural product detected from the skin array of natural product targets, particularly alkaloids, unprecedented in other biological systems.1

  2. Synthesis of Chiral Hydroxyl Phospholanes from D-mannitol and Their Use in Asymmetric Catalytic Reactions

    E-print Network

    Zhang, Xumu

    Synthesis of Chiral Hydroxyl Phospholanes from D-mannitol and Their Use in Asymmetric Catalytic Reactions Wenge Li, Zhaoguo Zhang, Dengming Xiao, and Xumu Zhang* Department of Chemistry, The Pennsylvania explored. Rate acceleration in the Baylis-Hillman reaction was observed when a hydroxyl phosphine was used

  3. Asymmetric synthesis of Crispine A: constructing tetrahydroisoquinoline scaffolds using pummerer cyclizations

    Technology Transfer Automated Retrieval System (TEKTRAN)

    For the first time, a concise, linear and protecting group-free stereoselective synthesis of both enantiomers of crispine A have been achieved in six steps with an overall yield of less than or equal to 20%,starting from commercially available veratraldehyde. Asymmetric Keck allylation and trifluoro...

  4. Asymmetric Catalytic Synthesis of P-Stereogenic Phosphines via a Nucleophilic Ruthenium Phosphido Complex

    E-print Network

    Toste, Dean

    Asymmetric Catalytic Synthesis of P-Stereogenic Phosphines via a Nucleophilic Ruthenium Phosphido reaction. On the basis of the strong basicity and nucleophilicity of previously reported iron and ruthenium cationic phosphine complex 2-BPh4. Deprotonation of this complex with KHMDS afforded ruthenium phosphido

  5. Chiral-Auxiliary-Mediated Asymmetric Synthesis of Tris-Heteroleptic Ruthenium Polypyridyl Complexes

    E-print Network

    Meggers, Eric

    Chiral-Auxiliary-Mediated Asymmetric Synthesis of Tris-Heteroleptic Ruthenium Polypyridyl Complexes ruthenium polypyridyl complexes lacking additional chirality in the organic ligand sphere relies solely for a typical tris-heteroleptic ruthenium complex (Figure 1). This complex contains 2,2-bipyridine (bpy), 5

  6. Synthesis and Application of New Ligands Derived from N-Heterocyclic Carbenes, Phosphines and Phosphites for Asymmetric Hydrogenations 

    E-print Network

    Khumsubdee, Sakunchai

    2013-11-05

    , especially on hydrogenation of "largely unfunctionalized" alkenes, for more than a decade. These substrates, however, could not be easily modified leading to limited applications for organic synthesis. As a result, asymmetric hydrogenations of substrates...

  7. Synthesis of ?-Chiral Butyrolactones by Highly Stereoselective Radical Transfer or Sequential Asymmetric Alkylations: Concise Preparation of Leupyrrin Moieties.

    PubMed

    Schrempp, Michael; Thiede, Sebastian; Herkommer, Daniel; Gansäuer, Andreas; Menche, Dirk

    2015-11-01

    Inspired by the bioactive natural metabolites leupyrrin?A1 and B1 , two novel stereoselective methods for the highly concise synthesis of densely substituted ?-chiral butyrolactones are reported. The first approach relies on an innovative three-step Ti(III) -catalyzed radical reaction that proceeds with excellent chemo-, regio-, and stereoselectivity. The alternative route utilizes sequential asymmetric alkylations and enables asymmetric synthesis of the authentic ?-tetrasubstituted butyrolactone motif of the leupyrrins in only four steps from commercially available substrates. PMID:26354047

  8. Bifunctional phase-transfer catalysis in the asymmetric synthesis of biologically active isoindolinones

    PubMed Central

    Di Mola, Antonia; Tiffner, Maximilian; Scorzelli, Francesco; Palombi, Laura; Filosa, Rosanna; De Caprariis, Paolo

    2015-01-01

    Summary New bifunctional chiral ammonium salts were investigated in an asymmetric cascade synthesis of a key building block for a variety of biologically relevant isoindolinones. With this chiral compound in hand, the development of further transformations allowed for the synthesis of diverse derivatives of high pharmaceutical value, such as the Belliotti (S)-PD172938 and arylated analogues with hypnotic sedative activity, obtained in good overall total yield (50%) and high enantiomeric purity (95% ee). The synthetic routes developed herein are particularly convenient in comparison with the current methods available in literature and are particularly promising for large scale applications.

  9. Asymmetric Synthetic Access to the Hetisine Alkaloids: Total Synthesis of (+)-Nominine

    PubMed Central

    Peese, Kevin M.

    2008-01-01

    A dual cycloaddition strategy for the synthesis of the hetisine alkaloids has been developed, illustrated by a concise asymmetric total synthesis of (+)-nominine (7). The approach relies on an early-stage intramolecular 1,3-dipolar cycloaddition of a 4-oxido-isoquinolinium betaine dipole with an ene–nitrile dipolarophile. Subsequent late-stage pyrrolidine-induced dienamine isomerization/Diels–Alder cascade allows for rapid construction of the carbon–nitrogen polycyclic skeleton within this class of C20-diterpenoid alkaloids. PMID:18046691

  10. New and Accurate Synthesis Formulas for Asymmetric Coplanar Stripline with an Infinitely Wide Strip

    NASA Astrophysics Data System (ADS)

    Guney, K.; Yildiz, C.; Kaya, S.; Turkmen, M.

    2009-02-01

    New and accurate synthesis formulas for the asymmetric coplanar stripline with an infinitely wide strip (ACPS-IWS) are presented. They are obtained by using a differential evolution algorithm (DEA) and particle swarm optimization (PSO) algorithm, and are useful to microwave engineers for accurately computing the physical dimensions of ACPS-IWS. The average percentage errors of the synthesis formulas found by using DEA and PSO are calculated to be 0.85% and 1.62%, respectively, for 4913 ACPS-IWS samples having different electrical parameters and physical dimensions, as compared with the results of quasi-static analysis.

  11. Catalytic, Enantioselective Synthesis of 1,2-anti Diols via Asymmetric Ring Opening/Cross Metathesis

    PubMed Central

    Hartung, John

    2014-01-01

    An enantioselective method for the synthesis of 1,2-anti diols has been developed. A cyclometallated chiral-at-Ru complex catalyzes the asymmetric ring opening/cross metathesis of di–oxygenated cyclobutenes, resulting in functionally rich synthetic building blocks. Syntheses of the insect pheromone (+)-endo brevicomin and monosaccharide ribose demonstrate the synthetic utility of the 1,2-anti diol fragments generated in the title reaction. PMID:24554613

  12. Asymmetric Synthesis of Fluorinated Isoindolinones through Palladium-Catalyzed Carbonylative Amination of Enantioenriched Benzylic Carbamates.

    PubMed

    Barrio, Pablo; Ibáñez, Ignacio; Herrera, Lidia; Román, Raquel; Catalán, Silvia; Fustero, Santos

    2015-08-01

    The asymmetric synthesis of fluorinated isoindolinones has been achieved by a palladium-catalyzed aminocarbonylation reaction of the corresponding ?-fluoroalkyl o-iodobenzylamines. A base-mediated anti ?-hydride elimination process was suggested to explain the partial erosion of the optical purity observed in some cases. This mechanistic rationale enabled the minimization of this partial racemization by fine-tuning the pKa of the base. PMID:26121312

  13. Asymmetric Synthesis of Fully Substituted Cyclopentane-Oxindoles through an Organocatalytic Triple Michael Domino Reaction

    PubMed Central

    Zou, Liang-Hua; Philipps, Arne R; Raabe, Gerhard; Enders, Dieter

    2015-01-01

    An efficient, highly stereoselective asymmetric synthesis of fully functionalized cyclopentanes bearing an oxindole moiety and several other functional groups in one pot has been developed. Key step is an organocatalytic triple Michael domino reaction forming three C–C bonds and six stereocenters, including a quaternary one. Starting from equimolar amounts of simple substrates, a high molecular complexity can be reached after a Wittig olefination in one pot. The new protocol can easily be scaled up to gram amounts. PMID:25470781

  14. Asymmetric synthesis of the carbapenam core from serine.

    PubMed

    Hart, Barry P; Verma, Sharad K; Rapoport, Henry

    2003-01-10

    The stereospecific synthesis of the functionalized carbapenam core 16 from the serine-derived trisubstituted pyrrolidine 9 is reported. The synthetic strategy relies on synthesizing an appropriately functionalized pyrrolidine, followed by an intramolecular azetidone formation utilizing a modified Mukiyama reagent. The efficient one-pot conversion of the benzenesulfonamide-protected pyrrolidine 9 to the Cbz-protected pyrrolidine 10 is also reported. PMID:12515481

  15. Asymmetric Catalysis with Ethylene. Synthesis of Functionalized Chiral Enolates.

    PubMed

    Biswas, Souvagya; Page, Jordan P; Dewese, Kendra R; RajanBabu, T V

    2015-11-18

    Trialkylsilyl enol ethers are versatile intermediates often used as enolate surrogates for the synthesis of carbonyl compounds. Yet there are no reports of broadly applicable, catalytic methods for the synthesis of chiral silyl enol ethers carrying latent functionalities useful for synthetic operations beyond the many possible reactions of the silyl enol ether moiety itself. Here we report a general procedure for highly catalytic (substrate:catalyst ratio up to 1000:1) and enantioselective (92% to 98% major enantiomer) synthesis of such compounds bearing a vinyl group at a chiral carbon at the ?-position. The reactions, run under ambient conditions, use trialkylsiloxy-1,3-dienes and ethylene (1 atm) as precursors and readily available (bis-phosphine)-cobalt(II) complexes as catalysts. The silyl enolates can be readily converted into novel enantiopure vinyl triflates, a class of highly versatile cross-coupling reagents, enabling the syntheses of other enantiomerically pure, stereodefined trisubstituted alkene intermediates not easily accessible by current methods. Examples of Kumada, Stille, and Suzuki coupling reactions are illustrated. PMID:26529467

  16. The Catalytic Asymmetric Total Synthesis of Elatol David E. White, Ian C. Stewart, Robert H. Grubbs, and Brian M. Stoltz*

    E-print Network

    Stoltz, Brian M.

    S1 The Catalytic Asymmetric Total Synthesis of Elatol David E. White, Ian C. Stewart, Robert H. Grubbs, and Brian M. Stoltz* The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division, triethylamine, and N,N,N,N- tetramethylethylenediamine were obtained from distillation over CaH2. Methyl vinyl

  17. One-Pot Catalysis Using a Chiral Iridium Complex/Brønsted Base: Catalytic Asymmetric Synthesis of Catalponol.

    PubMed

    Suzuki, Takeyuki; Ismiyarto; Ishizaka, Yuka; Zhou, Da-Yang; Asano, Kaori; Sasai, Hiroaki

    2015-11-01

    Tandem asymmetric hydrogen transfer oxidation/aldol condensation under relay catalysis of a chiral iridium complex/achiral Brønsted base binary system is described for the synthesis of ?-benzylidene-?-hydroxytetralones with high ee's. A two-step synthesis of catalponol was achieved using this sequential methodology together with regio- and stereoselective hydroboration. PMID:26496409

  18. Toward a real synthesis of quantum and relativity theories: experimental evidence for absolute simultaneity

    E-print Network

    S. A. Emelyanov

    2013-01-16

    We have demonstrated spatially-discontinuous jumps of electrons at a distance as long as about 1cm. The effect occurs in a modified integer quantum Hall system consisted of a great number of extended Laughlin-Halperin-type states. Our observations directly contradict the no-aether Einstein's interpretation of special relativity together with the Minkowski's model of spacetime. However they are consistent with the aether-related Lorentz-Poincare's interpretation that allows absolute simultaneity. We thus strongly challenge the fundamental status of Lorentz invariance and hence break the basic argument against de Broglie-Bohm realistic quantum theory. We argue that both de Broglie-Bohm and Lorentz-Poincare theories are capable of providing a real synthesis of quantum and relativity theories. The synthesis is of such kind that quantum theory appears the most fundamental physical theory for which relativity is only a limiting case. In accordance with this hierarchy, quantum theory naturally resolves the problem of aether in Lorentz-Poincare's relativity. The aether could be a deeper Bohm-type undivided quantum pre-space, the relevance of which directly follows from our observations.

  19. Chemo-Enzymatic Synthesis of (13)C Labeled Complex N-Glycans As Internal Standards for the Absolute Glycan Quantification by Mass Spectrometry.

    PubMed

    Echeverria, Begoña; Etxebarria, Juan; Ruiz, Nerea; Hernandez, Álvaro; Calvo, Javier; Haberger, Markus; Reusch, Dietmar; Reichardt, Niels-Christian

    2015-11-17

    Methods for the absolute quantification of glycans are needed in glycoproteomics, during development and production of biopharmaceuticals and for the clinical analysis of glycan disease markers. Here we present a strategy for the chemo-enzymatic synthesis of (13)C labeled N-glycan libraries and provide an example for their use as internal standards in the profiling and absolute quantification of mAb glycans by matrix-assisted laser desorption ionization-time-of-flight (MALDI-TOF) mass spectrometry. A synthetic biantennary glycan precursor was (13)C-labeled on all four amino sugar residues and enzymatically derivatized to produce a library of 15 glycan isotopologues with a mass increment of 8 Da over the natural products. Asymmetrically elongated glycans were accessible by performing enzymatic reactions on partially protected UV-absorbing intermediates, subsequent fractionation by preparative HPLC, and final hydrogenation. Using a preformulated mixture of eight internal standards, we quantified the glycans in a monoclonal therapeutic antibody with excellent precision and speed. PMID:26482441

  20. Ate complexes of secondary boronic esters as chiral organometallic-type nucleophiles for asymmetric synthesis.

    PubMed

    Larouche-Gauthier, Robin; Elford, Tim G; Aggarwal, Varinder K

    2011-10-26

    The addition of an aryllithium reagent to a secondary boronic ester leads to an intermediate boron-ate complex that behaves as a chiral nucleophile, reacting with a broad range of electrophiles with inversion of stereochemistry. Depending on the electrophile, the C-B bond can be converted into C-I, C-Br, C-Cl, C-N, C-O, and C-C, all with very high levels of stereocontrol. This discovery now adds a new, readily available, configurationally stable, chiral organometallic-type reagent to the arsenal of methods for use in asymmetric organic synthesis. PMID:21939203

  1. Stereocontrolled asymmetric synthesis of alpha-hydroxy-beta-amino acids. A stereodivergent approach.

    PubMed

    Aoyagi, Y; Jain, R P; Williams, R M

    2001-04-18

    The stereocontrolled asymmetric synthesis of alpha-hydroxy-beta-amino acids has been investigated via the Lewis acid-promoted cyanation of (5R,6S)-2-acetoxy-4-(benzyloxycarbonyl)-5,6-diphenyl-2,3,5,6-tetrahydro-4H-1,4-oxazines with trimethylsilyl cyanide. Base-catalyzed hydrolysis of the resulting cyano compounds proceeds with excellent stereoselectivity, providing access to diastereomerically pure oxazine-2-carboxylic acids which were readily converted to each enantiomer of the alpha-hydroxy-beta-amino acids isothreonine and nor-C-statine. PMID:11472118

  2. Multicomponent synthesis of chiral bidentate unsymmetrical unsaturated N-heterocyclic carbenes: copper-catalyzed asymmetric C-C bond formation.

    PubMed

    Jahier-Diallo, Claire; Morin, Marie S T; Queval, Pierre; Rouen, Mathieu; Artur, Isabelle; Querard, Pierre; Toupet, Loic; Crévisy, Christophe; Baslé, Olivier; Mauduit, Marc

    2015-01-12

    A multicomponent strategy was applied to the synthesis of chiral bidentate unsaturated hydroxyalkyl- and carboxyalkyl-N-heterocyclic carbene (NHC) precursors. The newly developed low-cost chiral ligands derived from amino alcohols and amino acids were evaluated in copper-catalyzed asymmetric conjugated addition and asymmetric allylic alkylation, which afforded the desired tertiary and quaternary carbon stereocenters with excellent regio- and enantioselectivities (up to 99:1 e.r.). PMID:25421857

  3. Multi-component Cycloaddition Approaches in the Catalytic Asymmetric Synthesis of Alkaloid Targets†

    PubMed Central

    Perreault, Stéphane; Rovis, Tomislav

    2010-01-01

    Cycloaddition reactions are attractive strategies for rapid formation of molecular complexity in organic synthesis as multiple bonds are formed in a single process. To this end, several research groups have been actively involved in the development of catalytic methods to activate readily accessible ?-components to achieve cycloadditions. However, the use of C-N ?-components for the formation of heterocycles by these processes is less well developed. It has been previously demonstrated that the combination of different isocyanates with two alkynes yields pyridones of several types by metal-catalyzed [2+2+2] cycloadditions. The potential of this chemistry has been extended to alkenes as C-C ?-components, allowing the formation of sp3-stereocenters. In this tutorial review directed towards [n+2+2] cycloaddition of heterocumulenes, alkynes and alkenes, the recent advances in catalytic asymmetric synthesis of indolizidine, quinolizidine and azocine skeletons are discussed. PMID:19847348

  4. Expanding the threonine aldolase toolbox for the asymmetric synthesis of tertiary ?-amino acids.

    PubMed

    Fesko, Kateryna; Strohmeier, Gernot A; Breinbauer, Rolf

    2015-11-01

    The direct biochemical synthesis of tertiary ?-amino acids with a wide range of diversity was recently reported using natural threonine aldolases LTA from Aeromonas jandei and DTA from Pseudomonas sp. Here, we describe the identification of five novel threonine aldolases which accept alanine and serine as amino acid donors. The enzymes were found by sequence database analysis using known aldolases as template. All enzymes were overexpressed in Escherichia coli and purified, and their biochemical properties were characterized. The new enantiocomplementary L- and D-threonine aldolases catalyze the asymmetric synthesis of ?-hydroxy ?-methyl- and ?-hydroxymethyl-?-amino acids with good conversion and perfect enantioselectivity at ?-carbon of the products (e.e. >99 %). The structural basis for the broad donor specificity of these threonine aldolases is analyzed based on crystal structure alignments and amino acid sequences comparison. PMID:26189018

  5. Engineering methylaspartate ammonia lyase for the asymmetric synthesis of unnatural amino acids

    NASA Astrophysics Data System (ADS)

    Raj, Hans; Szyma?ski, Wiktor; de Villiers, Jandré; Rozeboom, Henriëtte J.; Veetil, Vinod Puthan; Reis, Carlos R.; de Villiers, Marianne; Dekker, Frank J.; de Wildeman, Stefaan; Quax, Wim J.; Thunnissen, Andy-Mark W. H.; Feringa, Ben L.; Janssen, Dick B.; Poelarends, Gerrit J.

    2012-06-01

    The redesign of enzymes to produce catalysts for a predefined transformation remains a major challenge in protein engineering. Here, we describe the structure-based engineering of methylaspartate ammonia lyase (which in nature catalyses the conversion of 3-methylaspartate to ammonia and 2-methylfumarate) to accept a variety of substituted amines and fumarates and catalyse the asymmetric synthesis of aspartic acid derivatives. We obtained two single-active-site mutants, one exhibiting a wide nucleophile scope including structurally diverse linear and cyclic alkylamines and one with broad electrophile scope including fumarate derivatives with alkyl, aryl, alkoxy, aryloxy, alkylthio and arylthio substituents at the C2 position. Both mutants have an enlarged active site that accommodates the new substrates while retaining the high stereo- and regioselectivity of the wild-type enzyme. As an example, we demonstrate a highly enantio- and diastereoselective synthesis of threo-3-benzyloxyaspartate (an important inhibitor of neuronal excitatory glutamate transporters in the brain).

  6. The use of tritiated water to measure absolute rates of hepatic glycogen synthesis.

    PubMed

    Postle, A D; Bloxham, D P

    1980-10-15

    Glucogen synthesis in rat liver in vivo was measured by the incorporation of 3H from 3H2O into glycogen. In meal-fed rats incorporation and the incorporation of 3H into glycogen was linear up to 100 min. Before feeding glycogen concentration and the incorporation of 3H were both low; and both rose on feeding to give maximal values after 2-3h. The glycogen concentration was maintained for a further 5h but the incorporation of 3H rapidly declined to pre-feeding values. This shows that glycogen turnover was low in the post-prandial rat. Streptozotocin diabetes decreased the rise in glycogen concentration on feeding and had a similar effect on 3H2O incorporation. Both effects were reversed by insulin administration. The number of 3H atoms incorporated per glycogen glucose moiety formed in biosynthetic experiments (2.84 +/- 0.47) was relatively constant and allowed absolute biosynthetic rates to be calculated. Degradation of glucose from glycogen labelled by 3H2O showed that most of the 3H was located at C-2 and C-5. The incorporation would arise by rapid equilibration of hexose phosphates through phosphoglucose isomerase, transaldolase and triose phosphate isomerase. PMID:7305913

  7. Synthesis and photophysicochemical studies of poly(ethylene glycol) conjugated symmetrical and asymmetrical zinc phthalocyanines

    NASA Astrophysics Data System (ADS)

    Dinçer, Hatice; Mert, Humeyra; Çal??kan, Emel; Atmaca, Göknur Ya?a; Erdo?mu?, Ali

    2015-12-01

    Synthesis and characterization of poly(ethylene glycol) conjugated symmetrical and asymmetrical zinc phthalocyanines (ZnPcs) is described. Copper (I) catalyzed azide-alkyne cycloaddition (CuAAC) click reaction between azide functional methoxypoly(ethylene glycol) (mPEG-N3) and tetra terminal alkynyl substituted ZnPc yields star polymer with ZnPc core. Furthermore, CuAAC click reaction between asymmetrically terminal alkynyl substituted zinc phthalocyanine (aZnPc) and mPEG-N3 yields aZnPc end functionalized PEG. Spectral, photophysical (fluorescence quantum yield), photochemical (singlet oxygen (??), and photodegradation quantum yield (?d) properties of the symmetrically, and asymmetrically PEGylated ZnPcs are investigated to be used as sensitizers in photodynamic therapy (PDT). The quantum yield values of fluorescence (?F) and singlet oxygen generation (??) for water soluble symmetrically PEGylated ZnPc in aqueous solution are calculated as 0.01 and 0.14 respectively, suggesting its potential as photosensitizer in PDT treatment.

  8. Regio- and enantioselective synthesis of N-substituted pyrazoles by rhodium-catalyzed asymmetric addition to allenes.

    PubMed

    Haydl, Alexander M; Xu, Kun; Breit, Bernhard

    2015-06-01

    The rhodium-catalyzed asymmetric N-selective coupling of pyrazole derivatives with terminal allenes gives access to enantioenriched secondary and tertiary allylic pyrazoles, which can be employed for the synthesis of medicinally important targets. The reaction tolerates a large variety of functional groups and labelling experiments gave insights into the reaction mechanism. This new methodology was further applied in a highly efficient synthesis of JAK?1/2 inhibitor (R)-ruxolitinib. PMID:25926026

  9. Asymmetric Synthesis of (-)-Incarvillateine Employing an Intramolecular Alkylation via Rh-Catalyzed Olefinic C-H Bond Activation

    SciTech Connect

    Tsai, Andy; Bergman, Robert; Ellman, Jonathan

    2008-02-18

    An asymmetric total synthesis of (-)-incarvillateine, a natural product having potent analgesic properties, has been achieved in 11 steps and 15.4% overall yield. The key step is a rhodium-catalyzed intramolecular alkylation of an olefinic C-H bond to set two stereocenters. Additionally, this transformation produces an exocyclic, tetrasubstituted alkene through which the bicyclic piperidine moiety can readily be accessed.

  10. Catalytic asymmetric synthesis of butane diacetal-protected (4S,5S)-dihydroxycyclohexen-1-one and use in natural product synthesis.

    PubMed

    Burns, David J; Hachisu, Shuji; O'Brien, Peter; Taylor, Richard J K

    2012-10-14

    Due to the lack of availability of unnatural (+)-quinic acid as a starting material, a 6-step synthesis of butane diacetal-protected (4S,5S)-dihydroxycyclohexen-1-one (formally derived from (+)-quinic acid) has been devised. The key catalytic asymmetric step involves a chiral Co-salen-catalysed epoxide ring-opening reaction. (4S,5S)-Dihydroxycyclohexen-1-one was utilised in the synthesis of two cyclohexenone natural products isolated from the mycelia of Lasiodiplodia theobromae. PMID:22930235

  11. Asymmetric synthesis of anti-aldol segments via a nonaldol route: synthetic applications to statines and (-)-tetrahydrolipstatin.

    PubMed

    Ghosh, Arun K; Shurrush, Khriesto; Kulkarni, Sarang

    2009-06-19

    An asymmetric synthesis of anti-aldol segments via a nonaldol route is described. The strategy involves a highly diastereoselective synthesis of functionalized tetrahydrofuran derivatives from optically active 4-phenylbutyrolactone. Treatment of the tetrahydrofuran derivatives with a Lewis acid and acetic anhydride provided the corresponding ring-opened styrene derivatives. Oxidative cleavage of the styrene derivatives provided access to the anti-aldol segments. The utility of this methodology was demonstrated by the synthesis of statine derivatives and pancreatic lipase inhibitor, (-)-tetrahydrolipstatin. PMID:19438217

  12. Haloperidol metabolite II prodrug: asymmetric synthesis and biological evaluation on rat C6 glioma cells.

    PubMed

    Sozio, Piera; Fiorito, Jole; Di Giacomo, Viviana; Di Stefano, Antonio; Marinelli, Lisa; Cacciatore, Ivana; Cataldi, Amelia; Pacella, Stephanie; Turkez, Hasan; Parenti, Carmela; Rescifina, Antonio; Marrazzo, Agostino

    2015-01-27

    In a previous work we reported the antiproliferative effects of (±)-MRJF4, a novel haloperidol metabolite II (HP-mII) (a sigma-1 antagonist and sigma-2 agonist) prodrug, obtained through conjugation to 4-phenylbutyric acid (PhBA) [a histone deacetylase inhibitor (HDACi)] via an ester bond. As a continuation of this work, here we report the asymmetric synthesis of compounds (R)-(+)-MRJF4 and (S)-(-)-MRJF4 and the evaluation of their biological activity on rat C6 glioma cells, derived from glioblastoma multiforme (GBM), which is the most common and deadliest central nervous system (CNS) invasive malignancy. Favourable physicochemical properties, high permeability in the parallel artificial membrane permeability assay (PAMPA), good enzymatic and chemical stability, in vivo anticancer activity, associated with the capacity to reduce cell viability and to increase cell death by apoptosis, render compound (R)-(+)-MRJF4 a promising candidate for the development of a useful therapeutic for gliomas therapy. PMID:25461306

  13. A Simple Synthesis of Alliin and allo-Alliin: X-ray Diffraction Analysis and Determination of Their Absolute Configurations.

    PubMed

    Hakamata, Wataru; Koyama, Ryosuke; Tanida, Mizuki; Haga, Tomomi; Hirano, Takako; Akao, Makoto; Kumagai, Hitomi; Nishio, Toshiyuki

    2015-12-23

    A simple method for the isolation of the bioactive compound alliin from garlic, as well as a method for the synthesis of diastereomerically pure alliin and allo-alliin on a preparative laboratory scale, was developed. The absolute configuration of the sulfur atom in alliin and allo-alliin was assigned on the basis of enzyme reactivity, optical rotatory dispersion, and circular dichroism analyses. A comparison of the results from these analyses, in combination with an X-ray diffraction study on a protected allo-alliin derivative, revealed S and R configurations of the sulfur atoms in alliin and allo-alliin, respectively. In addition, the same (1)H NMR spectrum was observed for synthetic and natural alliin. The absolute configuration of natural alliin was assigned for the first time on the basis of the NMR spectrum and X-ray coordinates. PMID:26638713

  14. Synthesis of Long, Palladium End-Capped Polyynes through the Use of Asymmetric 1-Iodopolyynes.

    PubMed

    Pigulski, Bart?omiej; Gulia, Nurbey; Szafert, S?awomir

    2015-12-01

    The synthesis of a unique series of long, asymmetric 1-iodopolyynes (1-Cn I and 2-Cn I) with the sp-hybridized carbon chain up to a decapentayne is reported. These compounds were then used as substrates in reactions with Pd(PPh3 )4 leading to another series of palladium end-capped polyynes, which were unstable in solution. Organometallic octatetraynes 1-C8 [Pd]I, 2-C8 [Pd]I, and decapentayne 1-C10 [Pd]I are palladium end-capped polyyne compounds with the longest carbon chains reported so far. All the complexes as well as their organic precursors were fully characterized by NMR, HRMS(ESI), IR, TGA-DTA, and UV/Vis techniques, and the X-ray crystal structures of two silyl-protected precursors and one palladium complex are presented. The synthetic approach for palladium species is envisioned as a general route for the synthesis of labile organometallic polyynes. PMID:26490174

  15. Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters

    E-print Network

    Fujiwara, Yuji

    Through the design and synthesis of a new chiral phosphepine, the first catalytic asymmetric method for the [3 + 2] cycloaddition of allenes with olefins has been developed that generates cyclopentenes that bear nitrogen-, ...

  16. Studies in asymmetric ?-lactone synthesis: extensions of the chiral nucleophile catalyzed aldol-lactonization (NCAL) reaction and new transformations of chlorinated ?-lactones 

    E-print Network

    Tennyson, Reginald L.

    2001-01-01

    Expansion of Wynberg's procedure for the asymmetric synthesis of ?-lactones has been extended to the use of in situ generated ketene. Reaction with dichlorinated aldehydes in the presence of quinidine yielded ?-lactone products in good yield (40...

  17. An advance on exploring N-tert-butanesulfinyl imines in asymmetric synthesis of chiral amines.

    PubMed

    Lin, Guo-Qiang; Xu, Ming-Hua; Zhong, Yu-Wu; Sun, Xing-Wen

    2008-07-01

    Although catalytic asymmetric synthesis has undergone tremendous growth in the last 30 years, chiral auxiliary-aided asymmetric synthesis continues to attract considerable attention. Chiral N- tert-butanesulfinamide, as pioneered by Ellman and co-workers, is undoubtedly one of the most efficient auxiliaries developed to date; it allows the preparation, through simple conversion, of a diverse range of enantiopure amines, which are ubiquitous in natural products and biologically active molecules. Following on from our studies of the SmI(2)-mediated asymmetric syntheses of alpha,gamma-substituted gamma-butyrolactones, we found that simple homocoupling of chiral N- tert-butanesulfinyl imines in the presence of SmI(2) produced enantiopure vicinal C2-symmetric diamines in high yield. In addition, C2-unsymmetric chiral diamines are readily prepared through SmI(2)-mediated cross-couplings of N- tert-butanesulfinyl imines and nitrones; these transformations represented the first successful examples of asymmetric cross-coupling between two different imine species. Subsequently, we discovered another useful reaction induced by SmI(2), the efficient cross-coupling of N- tert-butanesulfinyl imines and aldehydes, which provides ready access to enantiopure anti-1,2-amino alcohols. The synthetic applicability of this reaction was demonstrated through its use in the facile total syntheses of (3R,4S)-statine, d- erythro-sphinganine, (+)-CP-99,994, and (+)-L-733,060. The Zn/In-mediated allylation of chiral N- tert-butanesulfinyl imines yields homoallylic amines. After pondering the reaction mechanism, we developed optimal reaction conditions for reversing the stereogenic outcome, thereby allowing the preparation of enantiopure homoallylic amines of either handedness from single enantiomers of the (R)- or (S)-sulfinyl imine. When a benzoyl-substituted allyl bromide is used for allylation, the reaction proceeds smoothly to give 2-vinyl-substituted anti-1,2-amino alcohols in high yields and diastereoselectivities, another simple method for preparing enantiopure amino alcohols. We employed these reactions in the syntheses of enantiopure allylglycine, 3-allyl-isoindolinones, and (-)-cytoxazone. Further studies led to the discovery that the allylations of N- tert-butanesulfinyl aldimines can be performed in water. The reactions described in this Account are among the simplest and most efficient synthetic methods available for preparing enantio-enriched diamines, amino alcohols, homoallylic amines, and other amine derivatives. These reactions are additionally attractive because of the ready availability of the starting materials, the simplicity of the reaction conditions, and the high degree of stereochemical control. Their applications in the total syntheses of several biologically interesting molecules illustrate the versatility of these transformations; we hope that they will stimulate the development of new synthetic methods. PMID:18533688

  18. Controlling the Facial Selectivity of Asymmetric [4+2] Cyclo-additions: A Concise Synthesis of the cis-Decalin Core Structure of Superstolides A and B

    PubMed Central

    Chen, Lei; Hua, Zhengmao; Li, Gangqin; Jin, Zhendong

    2011-01-01

    Regio, stereo and facial selective [4+2] cycloadditions between highly activated vinyl sulfones and 1,3-dienes derived from (R)-4-t-butyldimethyl-silyloxy-2-cyclohexen-1-one provide a powerful approach for the asymmetric synthesis of compounds containing the bicyclo[2.2.2]octanone carbon skeleton. This new methodology has been successfully applied to the asymmetric synthesis of the cis-decalin core structure of the potent anticancer marine natural products superstolides A and B. PMID:21671636

  19. Asymmetric Synthesis of Vitamin D3 Analogues: Organocatalytic Desymmetrization Approach toward the A-Ring Precursor of Calcifediol.

    PubMed

    Wang, Haifeng; Yan, Linjie; Wu, Yan; Lu, Yipei; Chen, Fener

    2015-11-01

    A novel asymmetric synthesis has been developed for the construction of the A-ring of a chiral precursor to calcifediol. The highlights of this synthesis include (i) the introduction of the stereochemistry at the C5-position of the A-ring through the organocatalytic enantioselective desymmetrization of a prochiral cyclic anhydride using a bifunctional urea catalyst and (ii) the introduction of the exo-cyclic (Z)-dienol side chain by a tandem Claisen rearrangement/sulfoxide thermolysis of an allylic alcohol. PMID:26507192

  20. Synthesis, resolution, and determination of absolute configuration of protected ?-ethynylphenylalanine enantiomers.

    PubMed

    Benfodda, Z; Bénimélis, D; Jean, M; Naubron, J-V; Rolland, V; Meffre, P

    2015-05-01

    Racemic-protected ?-ethynylphenylalanine was synthesized from DL-2-benzylserine using ?-benzylserinal as key intermediate and was successfully resolved by HPLC on a chiral stationary phase at a semipreparative scale. The absolute configuration of both enantiomers was determined by vibrational circular dichroism. PMID:25618753

  1. Synthesis of Phosphorescent Asymmetrically ?-Extended Porphyrins for Two-Photon Applications

    PubMed Central

    2015-01-01

    Significant effort has been directed in recent years toward porphyrins with enhanced two-photon absorption (2PA). However, the properties of their triplet states, which are central to many applications, have rarely been examined in parallel. Here we report the synthesis of asymmetrically ?-extended platinum(II) and palladium(II) porphyrins, whose 2PA into single-photon-absorbing states is enhanced as a result of the broken center-of-inversion symmetry and whose triplet states can be monitored by room-temperature phosphorescence. 5,15-Diaryl-syn-dibenzoporphyrins (DBPs) and syn-dinaphthoporphyrins (DNPs) were synthesized by [2 + 2] condensation of the corresponding dipyrromethanes and subsequent oxidative aromatization. Butoxycarbonyl groups on the meso-aryl rings render these porphyrins well-soluble in a range of organic solvents, while 5,15-meso-aryl substitution causes minimal nonplanar distortion of the macrocycle, ensuring high triplet emissivity. A syn-DBP bearing four alkoxycarbonyl groups in the benzo rings and possessing a large static dipole moment was also synthesized. Photophysical properties (2PA brightness and phosphorescence quantum yields and lifetimes) of the new porphyrins were measured, and their ground-state structures were determined by DFT calculations and/or X-ray analysis. The developed synthetic methods should facilitate the construction of ?-extended porphyrins for applications requiring high two-photon triplet action cross sections. PMID:25157580

  2. Highly Asymmetrical Glycerol Diether Bolalipids: Synthesis and Temperature-Dependent Aggregation Behavior.

    PubMed

    Markowski, Thomas; Drescher, Simon; Förster, Günter; Lechner, Bob-Dan; Meister, Annette; Blume, Alfred; Dobner, Bodo

    2015-10-01

    In the present work, we describe the synthesis and temperature-dependent aggregation behavior of two examples of a new class of highly asymmetrical glycerol diether bolaphospholipids. The bolalipids contain a long alkyl chain (C32) bound to glycerol in the sn-3 position, carrying a hydroxyl group at the ? position. The C16 alkyl chain in the sn-2 position either possesses a racemic methyl branch at the 10 position of the short alkyl chain (lipid II) or does not (lipid I). The sn-1 position of the glycerol is linked to a zwitterionic phosphocholine moiety. The temperature-dependent aggregation behavior of both bolalipids was studied using differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and X-ray scattering. Aggregate structures were visualized by transmission electron microscopy (TEM). We show that both bolalipids self-assemble into large lamellar sheetlike aggregates. Closed lipid vesicles or other aggregate structures such as tubes or nanofibers, as usually found for diglycerol tetraether lipids, were not observed. Within the lamellae the bolalipid molecules are arranged in an antiparallel (interdigitated) orientation. Lipid I, without an additional methyl moiety in the short alkyl chain, shows a lamellar phase with high crystallinity up to a temperature of 34 °C, which was not observed before for other phospholipids. PMID:26366715

  3. Asymmetric Synthesis of ?-Substituted ?-Methylenebutyro- lactones via TRIP-Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of (S)-(?)-Hydroxymatairesinol

    PubMed Central

    Fuchs, Michael; Schober, Markus; Orthaber, Andreas; Faber, Kurt

    2013-01-01

    Asymmetric allylation of (hetero)aromatic aldehydes by a zinc(II)-allylbutyrolactone species catalyzed by a chiral BINOL-type phosphoric acid gave ?-substituted ?-methylenebutyrolactones in 68 to >99% ee and 52–91% isolated yield. DFT studies on the intermediate Zn2+-complex – crucial for chiral induction – suggest a six-membered ring intermediate, which allows the phosphoric acid moiety to activate the aldehyde. The methodology was applied to the synthesis of the antitumour natural product (S)-(?)-hydroxymatairesinol. PMID:24415960

  4. Asymmetric Synthesis of Spirocyclic 2-Benzopyrans for Positron Emission Tomography of ?1 Receptors in the Brain

    PubMed Central

    Holl, Katharina; Schepmann, Dirk; Fischer, Steffen; Ludwig, Friedrich-Alexander; Hiller, Achim; Donat, Cornelius K.; Deuther-Conrad, Winnie; Brust, Peter; Wünsch, Bernhard

    2014-01-01

    Sharpless asymmetric dihydroxylation of styrene derivative 6 afforded chiral triols (R)-7 and (S)-7, which were cyclized with tosyl chloride in the presence of Bu2SnO to provide 2-benzopyrans (R)-4 and (S)-4 with high regioselectivity. The additional hydroxy moiety in the 4-position was exploited for the introduction of various substituents. Williamson ether synthesis and replacement of the Boc protective group with a benzyl moiety led to potent ?1 ligands with high ?1/?2-selectivity. With exception of the ethoxy derivative 16, the (R)-configured enantiomers represent eutomers with eudismic ratios of up to 29 for the ester (R)-18. The methyl ether (R)-15 represents the most potent ?1 ligand of this series of compounds, with a Ki value of 1.2 nM and an eudismic ratio of 7. Tosylate (R)-21 was used as precursor for the radiosynthesis of [18F]-(R)-20, which was available by nucleophilic substitution with K[18F]F K222 carbonate complex. The radiochemical yield of [18F]-(R)-20 was 18%–20%, the radiochemical purity greater than 97% and the specific radioactivity 175–300 GBq/µmol. Although radiometabolites were detected in plasma, urine and liver samples, radiometabolites were not found in brain samples. After 30 min, the uptake of the radiotracer in the brain was 3.4% of injected dose per gram of tissue and could be reduced by coadministration of the ?1 antagonist haloperidol. [18F]-(R)-20 was able to label those regions of the brain, which were reported to have high density of ?1 receptors. PMID:24451404

  5. Synthesis of Ferrocene Oxazoline N,O ligands and Their Application in Asymmetric Ethyl- and Phenylzinc Additions to Aldehydes.

    PubMed

    Nottingham, Chris; Benson, Robert; Müller-Bunz, Helge; Guiry, Patrick J

    2015-10-16

    The synthesis of a range of novel gem-disubstituted ferrocene-oxazoline ligands and their application in both the asymmetric ethyl- and phenylzinc additions to aldehydes is reported. These studies reveal that gem-disubstitution of i-Pr-containing ferrocene oxazoline ligands results in increased enantioselectivity compared to their unsubstituted counterparts. Utilizing zinc catalysis, these ligands provided a wide range of secondary alcohols in yields of up to 93% with ee's of up to >99%. An interesting crystal structure of a ferrocene oxide-lithium tetramer showing lithium-nitrogen coordination in the solid state is also presented. PMID:26324068

  6. Core-structure-inspired asymmetric addition reactions: enantioselective synthesis of dihydrobenzoxazinone- and dihydroquinazolinone-based anti-HIV agents.

    PubMed

    Li, Shen; Ma, Jun-An

    2015-11-01

    Dihydrobenzoxazinones and dihydroquinazolinones are the core units present in many anti-HIV agents, such as Efavirenz, DPC 961, DPC 963, and DPC 083. All these molecules contain a trifluoromethyl moiety at the quaternary stereogenic carbon center with S configuration. The enantioselective addition of carbon nucleophiles to ketones or cyclic ketimines could serve as a key step to access these molecules. This tutorial review provides an overview of significant advances in the synthesis of dihydrobenzoxazinone- and dihydroquinazolinone-based anti-HIV agents and relative analogues, with an emphasis on asymmetric addition reactions for the establishment of the CF3-containing quaternary carbon centers. PMID:26177889

  7. Phosphine-Catalyzed Formation of Carbon-Sulfur Bonds: Catalytic Asymmetric Synthesis of gamma-Thioesters

    E-print Network

    Sun, Jianwei

    A method for catalytic asymmetric ? sulfenylation of carbonyl compounds has been developed. In the presence of an appropriate catalyst, thiols not only add to the ? position of allenoates, overcoming their propensity to ...

  8. The Construction of All-Carbon Quaternary Stereocenters by Use of Pd-Catalyzed Asymmetric Allylic Alkylation Reactions in Total Synthesis

    PubMed Central

    Hong, Allen Y.

    2014-01-01

    All-carbon quaternary stereocenters have posed significant challenges in the synthesis of complex natural products. These important structural motifs have inspired the development of broadly applicable palladium-catalyzed asymmetric allylic alkylation reactions of unstabilized non-biased enolates for the synthesis of enantioenriched ?-quaternary products. This microreview outlines key considerations in the application of palladium-catalyzed asymmetric allylic alkylation reactions and presents recent total syntheses of complex natural products that have employed these powerful transformations for the direct, catalytic, enantioselective construction of all-carbon quaternary stereocenters. PMID:24944521

  9. Asymmetric synthesis of trans-?-lactams by a Kinugasa reaction on water.

    PubMed

    Chen, Zhenling; Lin, Lili; Wang, Min; Liu, Xiaohua; Feng, Xiaoming

    2013-06-01

    The asymmetric Kinugasa reaction was performed on pure water for the first time without the need for any organic co-solvents. In contrast to most asymmetric Kinugasa reactions, trans-?-lactams were obtained as the major products in good yields, enantioselectivities, and diastereoselectivities (up to 90?% yield, 98?% ee, and >99:1 d.r.). This reaction is atom-economical, environmentally friendly, and affords synthetically useful but challenging products. PMID:23576446

  10. Easy Absolute Values? Absolutely

    ERIC Educational Resources Information Center

    Taylor, Sharon E.; Mittag, Kathleen Cage

    2015-01-01

    The authors teach a problem-solving course for preservice middle-grades education majors that includes concepts dealing with absolute-value computations, equations, and inequalities. Many of these students like mathematics and plan to teach it, so they are adept at symbolic manipulations. Getting them to think differently about a concept that they…

  11. Asymmetric synthesis of the HMG-CoA reductase inhibitor atorvastatin calcium: an organocatalytic anhydride desymmetrization and cyanide-free side chain elongation approach.

    PubMed

    Chen, Xiaofei; Xiong, Fangjun; Chen, Wenxue; He, Qiuqin; Chen, Fener

    2014-03-21

    An efficient asymmetric synthesis of atorvastatin calcium has been achieved from commercially available diethyl 3-hydroxyglutarate through a novel approach that involves an organocatalytic enantioselective cyclic anhydride desymmetrization to establish C(3) stereogenicity and cyanide-free assembly of C7 amino type side chain via C5+C2 strategy as the key transformations. PMID:24575888

  12. Correction: Studies towards asymmetric synthesis of 4(S)-11-dihydroxydocosahexaenoic acid (diHDHA) featuring cross-coupling of chiral stannane under mild conditions.

    PubMed

    Wang, Rui; He, Anyu; Ramu, Errabelli; Falck, John R

    2015-02-21

    Correction for 'Studies towards asymmetric synthesis of 4(S)-11-dihydroxydocosahexaenoic acid (diHDHA) featuring cross-coupling of chiral stannane under mild conditions' by Rui Wang et al., Org. Biomol. Chem., 2015, DOI: 10.1039/c4ob02324b. PMID:25609001

  13. Catalytic Asymmetric Iterative/Domino Aldehyde Cross-Aldol Reactions for the Rapid and Flexible Synthesis of 1,3-Polyols.

    PubMed

    Lin, Luqing; Yamamoto, Kumiko; Mitsunuma, Harunobu; Kanzaki, Yamato; Matsunaga, Shigeki; Kanai, Motomu

    2015-12-16

    We report here catalytic asymmetric iterative and domino cross-aldol reactions between aldehydes, endowed with a high level of robustness, flexibility, and generality. A Cu(I)-DTBM-SEGPHOS complex catalyzes an asymmetric cross-aldol reaction between acceptor aldehydes and boron enolates derived from donor aldehydes, which are generated through Ir-catalyzed isomerization of allyloxyboronates. The unit process can be repeated using the aldol products in turn as acceptor substrates for the subsequent asymmetric aldol reaction. The donor aldehydes and stereoselectivity can be flexibly switched in a stepwise manner for the double-aldol reaction. Furthermore, asymmetric triple- and quadruple-aldol reactions are possible in one-pot using the appropriate amounts of donors and amine additives, rapidly elongating the carbon skeleton with controlling up to eight stereocenters. The method should be useful for straightforward synthesis of enantiomerically and diastereomerically enriched 1,3-polyols. PMID:26632863

  14. ORGANIC SYNTHESIS. Comment on "Asymmetric syntheses of sceptrin and massadine and evidence for biosynthetic enantiodivergence".

    PubMed

    Sherman, David H; Tsukamoto, Sachiko; Williams, Robert M

    2015-07-10

    Ma et al. (Reports, 10 October 2014, p. 219) report asymmetric syntheses of sceptrin and massadine and, through a stereochemical reassignment, claim to "uncover enantiodivergence as a new biosynthetic paradigm for natural products." We challenge and clarify this claim with relevant examples from the literature of this well-known phenomenon of enantiodivergent congener biosynthesis within the same producing organism. PMID:26160938

  15. Enantiopure narrow bite-angle P-OP ligands: synthesis and catalytic performance in asymmetric hydroformylations and hydrogenations.

    PubMed

    Fernández-Pérez, Héctor; Benet-Buchholz, Jordi; Vidal-Ferran, Anton

    2014-11-17

    Herein is reported the preparation of a set of narrow bite-angle P-OP ligands the backbone of which contains a stereogenic carbon atom. The synthesis was based on a Corey-Bakshi-Shibata (CBS)-catalyzed asymmetric reduction of phosphomides. The structure of the resulting 1,1-P-OP ligands, which was selectively tuned through adequate combination of the configuration of the stereogenic carbon atom, its substituent, and the phosphite fragment, proved crucial for providing a rigid environment around the metal center, as evidenced by X-ray crystallography. These new ligands enabled very good catalytic properties in the Rh-mediated enantioselective hydrogenation and hydroformylation of challenging and model substrates (up to 99?%?ee). Whereas for asymmetric hydrogenation the optimal P-OP ligand depended on the substrate, for hydroformylation, a single ligand was the highest-performing one for almost all studied substrates: it contains an R-configured stereogenic carbon atom between the two phosphorus ligating groups, and an S-configured 3,3'-diphenyl-substituted biaryl unit. PMID:25335770

  16. A general strategy for the chemoenzymatic synthesis of asymmetrically branched N-glycans.

    PubMed

    Wang, Zhen; Chinoy, Zoeisha S; Ambre, Shailesh G; Peng, Wenjie; McBride, Ryan; de Vries, Robert P; Glushka, John; Paulson, James C; Boons, Geert-Jan

    2013-07-26

    A systematic, efficient means of producing diverse libraries of asymmetrically branched N-glycans is needed to investigate the specificities and biology of glycan-binding proteins. To that end, we describe a core pentasaccharide that at potential branching positions is modified by orthogonal protecting groups to allow selective attachment of specific saccharide moieties by chemical glycosylation. The appendages were selected so that the antenna of the resulting deprotected compounds could be selectively extended by glycosyltransferases to give libraries of asymmetrical multi-antennary glycans. The power of the methodology was demonstrated by the preparation of a series of complex oligosaccharides that were printed as microarrays and screened for binding to lectins and influenza-virus hemagglutinins, which showed that recognition is modulated by presentation of minimal epitopes in the context of complex N-glycans. PMID:23888036

  17. Asymmetric Allylic C-H Oxidation for the Synthesis of Chromans.

    PubMed

    Wang, Pu-Sheng; Liu, Peng; Zhai, Yu-Jia; Lin, Hua-Chen; Han, Zhi-Yong; Gong, Liu-Zhu

    2015-10-14

    An enantioselective intramolecular allylic C-H oxidation to generate optically active chromans has been accomplished under the cooperative catalysis of a palladium complex of chiral phosphoramidite ligand and 2-fluorobenzoic acid. Mechanistic studies suggest that this reaction commences with a Pd-catalyzed allylic C-H activation event and then undergoes asymmetric allylic alkoxylation. The synthetic significance of the method has been embodied by concisely building up a key chiral intermediate to access (+)-diversonol. PMID:26400002

  18. Asymmetric Synthesis of ?-Amino Amides by Catalytic Enantioconvergent 2-Aza-Cope Rearrangement.

    PubMed

    Goodman, C Guy; Johnson, Jeffrey S

    2015-11-25

    Dynamic kinetic resolutions of ?-stereogenic-?-formyl amides in asymmetric 2-aza-Cope rearrangements are described. Chiral phosphoric acids catalyze this rare example of a non-hydrogenative DKR of a ?-oxo acid derivative. The [3,3]-rearrangement occurs with high diastereo- and enantiocontrol, forming ?-imino amides that can be deprotected to the primary ?-amino amide or reduced to the corresponding diamine. PMID:26561873

  19. Coordinating Chiral Ionic Liquids: Design, Synthesis, and Application in Asymmetric Transfer Hydrogenation under Aqueous Conditions

    PubMed Central

    Vasiloiu, Maria; Gaertner, Peter; Zirbs, Ronald; Bica, Katharina

    2015-01-01

    Hydrophilic coordinating chiral ionic liquids with an amino alcohol substructure were developed and efficiently applied to the asymmetric reduction of ketones. Their careful design and adaptability to the desired reaction conditions allow for these chiral ionic liquids to be used as the sole source of chirality in a ruthenium-catalyzed transfer hydrogenation reaction of aromatic ketones. When used in this reaction system, these chiral ionic liquids afforded excellent yields and high enantioselectivities. PMID:26279638

  20. Catalytic asymmetric intramolecular homologation of ketones with ?-diazoesters: synthesis of cyclic ?-aryl/alkyl ?-ketoesters.

    PubMed

    Li, Wei; Tan, Fei; Hao, Xiaoyu; Wang, Gang; Tang, Yu; Liu, Xiaohua; Lin, Lili; Feng, Xiaoming

    2015-01-26

    A catalytic asymmetric intramolecular homologation of simple ketones with ?-diazoesters was firstly accomplished with a chiral N,N'-dioxide-Sc(OTf)3 complex. This method provides an efficient access to chiral cyclic ?-aryl/alkyl ?-ketoesters containing an all-carbon quaternary stereocenter. Under mild conditions, a variety of aryl- and alkyl-substituted ketone groups reacted with ?-diazoester groups smoothly through an intramolecular addition/rearrangement process, producing the ?-ketoesters in high yield and enantiomeric excess. PMID:25488490

  1. Asymmetric Synthesis of Medium-Sized Rings by Intramolecular Au(I)-Catalyzed Cyclopropanation

    PubMed Central

    Watson, Iain D. G.; Ritter, Stefanie; Toste, F. Dean

    2009-01-01

    An efficient method for the asymmetric gold(I)-catalyzed preparation of medium sized rings has been developed. The method provides 7- to 9-membered rings in excellent yield. High enantioselectivities can be achieved for 7- and 8-membered ring products employing chiral gold(I) complexes. The results provide insight into the mechanism, showing the fluxional nature of gold(I)-stabilized vinyl carbenoid intermediates. PMID:19161306

  2. A Petal-type Chiral NADH Model: Design, Synthesis and its Asymmetric Reduction

    PubMed Central

    Bai, Cui-Bing; Wang, Nai-Xing; Wang, Yan-Jing; Xing, Yalan; Zhang, Wei; Lan, Xing-Wang

    2015-01-01

    A new type of NADH model compound has been synthesized by an efficient and convenient method. This model compound exhibits high reactivity and enantioselectivity in asymmetric reduction reactions. The results show that chiral NADH model S could be effectively combined with Mg2+ to form ternary complexes. This novel C3 symmetrical NADH model is capable of fluorescence emission at 460?nm when excited at 377?nm. PMID:26648413

  3. Asymmetric Synthesis of Diverse Glycolic Acid Scaffolds via Dynamic Kinetic Resolution of ?-Keto Esters

    PubMed Central

    Steward, Kimberly M.; Corbett, Michael T.; Goodman, C. Guy; Johnson, Jeffrey S.

    2012-01-01

    The dynamic kinetic resolution of ?-keto esters via asymmetric transfer hydrogenation has been developed as a technique for the highly stereoselective construction of structurally diverse ?-substituted-?-hydroxy carboxylic acid derivatives. Through the development of a privileged m-terphenylsulfonamide for (arene)RuCl(monosulfonamide) complexes with a high affinity for selective ?-keto ester reduction, excellent levels of chemo-, diastereo-, and enantiocontrol can be realized in the reduction of ?-aryl- and ?-chloro-?-keto esters. PMID:23186551

  4. Synthesis and assessment of the antioxidant and antitumor properties of asymmetric curcumin analogues.

    PubMed

    Li, Qingyong; Chen, Jian; Luo, Shuyue; Xu, Jialin; Huang, Qiaoxian; Liu, Tianyu

    2015-03-26

    In this study, 12 asymmetric curcumin (CUR) analogues and 5 symmetric curcumin derivatives were synthesized, the antioxidant activity of these derivatives were evaluated by radicals 1,1-diphenyl-2-picryl-hydrazyl (DPPH) assay, 2,2-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) assay, ROO (TRAP) assay and O(2-) (NET) assay and anti-proliferative activities of these analogues were assessed against the human hepatoma cell line (SMMC-7721), the human breast cancer cell line (MCF-7) and the human prostate cancer cell lines (PC-3). Most of the asymmetric compounds showed stronger antioxidant activities than Vitamin C (Vc). Curcumin analogues reducing free radicals contain two reaction mechanisms: H-atom and electron transfer mechanisms. Compound 14 showed the most significant antioxidant activity compared with curcumin and other derivatives. Shorted the carbon chain of 14 can reduce the O-H bond dissociation enthalpy (BED) to improve the antioxidant activity. The antioxidant activity of 25 was similar to curcumin. All of the compounds performed better in an anti-proliferate assay than curcumin, especially compound 25, which exhibited the preferential cytotoxic activity against MCF-7 cells(25, IC50 = 9.11 ?M, curcumin, IC50 = 70.2 ?M). Considering these data, future studies should be performed to assess the therapeutic values of these asymmetric curcumin analogues. PMID:25728027

  5. Total Synthesis of Gobiusxanthin Stereoisomers and Their Application to Determination of Absolute Configurations of Natural Products: Revision of Reported Absolute Configuration of Epigobiusxanthin

    PubMed Central

    Yamano, Yumiko; Ematsu, Kotaro; Kurimoto, Hiromasa; Maoka, Takashi; Wada, Akimori

    2014-01-01

    (3R)-Gobiusxanthin stereoisomers (1a–d) were synthesized by stereoselective Wittig reaction of the (3R)-C15-acetylenic tri-n-butylphosphonium salt 7 with C25-apocarotenal stereoisomers 5a,b and 14a,b bearing four kinds of 3,6-dihydroxy-?-end groups. The validity of the reported stereochemistry of gobiusxanthin was demonstrated by the fact that the reported spectral data of natural gobiusxanthin were in agreement with those of synthetic (3R,3'S,6'R)-gobiusxanthin (1a). On the other hand, the reported CD spectral data of natural epigobiusxanthin, which has been assigned as (3R,3'R,6'R)-isomer (3'-epigobiusxanthin), were identical with those of synthetic (3R,3'S,6'S)-isomer 1d (6'-epigobiusxanthin) rather than those of the corresponding synthetic 3'-epi-isomer 1b. It was found that the stereochemistry at C3-position has little effect on the shape of their CD spectra. Thus, in order to reinforce the validity of the absolute configurations at C3-position of natural specimens, (3S,3'S,6'R)- and (3S,3'S,6'S)-stereoisomers 1e and 1f were also synthesized and a HPLC analytical method for four stereoisomers was established by using a column carrying a chiral stationary phase. The HPLC analysis has proven that the stereochemistry of the natural epigobiusxanthin is 3R,3'S,6'S. PMID:25561412

  6. Studies towards asymmetric synthesis of 4(S)-11-dihydroxydocosahexaenoic acid (diHDHA) featuring cross-coupling of chiral stannane under mild conditions.

    PubMed

    Wang, Rui; He, Anyu; Ramu, Errabelli; Falck, John R

    2015-02-14

    An efficient and asymmetric synthetic approach towards one of the biologically interesting 4(S)-11-diHDHA derivatives was developed. This process mainly relied on two reactions, one is the copper-catalyzed mild cross-coupling that allows for the efficient construction of a chiral ?-alkynyl ?-hydroxy motif and another is the synthesis of chiral ?-hydroxy ?-stannanes that has previously been developed by our group featuring the asymmetric stannylation using the well-established tributyltin hydride/diethyl zinc system from an aldehyde. PMID:25425336

  7. A highly enantioselective Biginelli reaction using self-assembled methanoproline-thiourea organocatalysts: asymmetric synthesis of 6-isopropyl-3,4-dihydropyrimidines.

    PubMed

    Hang, Zhijun; Zhu, Jun; Lian, Xiang; Xu, Peng; Yu, Han; Han, Sheng

    2015-12-15

    An efficient self-assembled methanoproline-thiourea organocatalyst for the synthesis of optically active 6-isopropyl-3,4-dihydro-pyrimidines via an asymmetric Biginelli reaction was developed, which is superior to the individual precatalyst. A wide range of optically active 6-isopropyl-3,4-dihydropyrimidines with remarkable pharmacological interest was obtained in high yields with excellent enantioselectivities (up to 99% ee). A plausible transition state has been proposed to explain the origin of the activation and the asymmetric induction. PMID:26498376

  8. Catalytic Asymmetric Synthesis of Branched Chiral Allylic Phenyl Ethers from (E)-Allylic Alcohols

    PubMed Central

    Olson, Angela C.; Overman, Larry E.; Sneddon, Helen F.; Ziller, Joseph W.

    2013-01-01

    The first di-?-amidate dipalladium complexes and a new di-?-carboxylate dipalladium complex of the COP (cobalt oxazoline palladacycle) palladium(II) catalyst family are reported and characterized crystallographically. The di-?-amidate complex 3 or its enantiomer (ent-3) are the first asymmetric catalysts that allow commercially available, or readily accessible, (E)-2-alkene-1-ols to be transformed to enantioenriched branched allylic aryl ethers upon reaction of their trichloroacetimidate derivatives with phenols. The 3-aryloxy-1-alkene products are formed in high enantiomeric purity (typically 90–98% ee) and useful yields (61–88%). PMID:23795152

  9. Facile Synthesis of Hierarchical Mesoporous Honeycomb-like NiO for Aqueous Asymmetric Supercapacitors.

    PubMed

    Ren, Xiaochuan; Guo, Chunli; Xu, Liqiang; Li, Taotao; Hou, Lifeng; Wei, Yinghui

    2015-09-16

    Three-dimensional (3D) hierarchical nanostructures have been demonstrated as one of the most ideal electrode materials in energy storage systems due to the synergistic combination of the advantages of both nanostructures and microstructures. In this study, the honeycomb-like mesoporous NiO microspheres as promising cathode materials for supercapacitors have been achieved using a hydrothermal reaction, followed by an annealing process. The electrochemical tests demonstrate the highest specific capacitance of 1250 F g(-1) at 1 A g(-1). Even at 5 A g(-1), a specific capacitance of 945 F g(-1) with 88.4% retention after 3500 cycles was obtained. In addition, the 3D porous graphene (reduced graphene oxide, rGO) has been prepared as an anode material for supercapacitors, which displays a good capacitance performance of 302 F g(-1) at 1 A g(-1). An asymmetric supercapacitor has been successfully fabricated based on the honeycomb-like NiO and rGO. The asymmetric supercapacitor achieves a remarkable performance with a specific capacitance of 74.4 F g(-1), an energy density of 23.25 Wh kg(-1), and a power density of 9.3 kW kg(-1), which is able to light up a light-emitting diode. PMID:26301430

  10. Asymmetric epoxidation of cis-alkenes mediated by iminium salts: highly enantioselective synthesis of levcromakalim.

    PubMed

    Page, Philip C Bulman; Buckley, Benjamin R; Heaney, Harry; Blacker, A John

    2005-02-01

    [reaction: see text] A range of cis-substituted olefins has been epoxidized with a new dihydroisoquinolinium salt catalyst, using tetraphenylphosphonium monoperoxysulfate as the stoichiometric oxidant, giving ee's of up to 97%. The reaction has been used as the key step in an enantioselective synthesis of the antihypertensive agent levcromakalim. PMID:15673243

  11. Synthesis of axially chiral gold complexes and their applications in asymmetric catalyses

    PubMed Central

    Sun, Yin-wei

    2013-01-01

    Summary Several novel chiral N-heterocyclic carbene and phosphine ligands were prepared from (S)-BINOL. Moreover, their ligated Au complexes were also successfully synthesized and characterized by X-ray crystal diffraction. A weak gold-? interaction between the Au atom and the aromatic ring in these gold complexes was identified. Furthermore, we confirmed the formation of a pair of diastereomeric isomers in NHC gold complexes bearing an axially chiral binaphthyl moiety derived from the hindered rotation around C–C and C–N bonds. In the asymmetric intramolecular hydroamination reaction most of these chiral Au(I) complexes showed good catalytic activities towards olefins tethered with a NHTs functional group to give the corresponding product in moderate yields and up to 29% ee. PMID:24204435

  12. Catalytic, asymmetric, and stereodivergent synthesis of non-symmetric ?,?-diaryl-?-amino acids.

    PubMed

    Molinaro, Carmela; Scott, Jeremy P; Shevlin, Michael; Wise, Christopher; Ménard, Alain; Gibb, Andrew; Junker, Ellyn M; Lieberman, David

    2015-01-21

    We report a concise, enantio- and diastereoselective route to novel nonsymmetrically substituted N-protected ?,?-diaryl-?-amino acids and esters, through the asymmetric hydrogenation of tetrasubstituted olefins, some of the most challenging examples in the field. Stereoselective generation of an E- or Z-enol tosylate, when combined with stereoretentive Suzuki-Miyaura cross-coupling and enantioselective hydrogenation catalyzed by (NBD)2RhBF4 and a Josiphos ligand, allows for full control over the two vicinal stereogenic centers. High yields and excellent enantioselectivities (up to 99% ee) were obtained for a variety of N-acetyl, N-methoxycarbonyl, and N-Boc ?,?-diaryldehydroamino acids, containing a diverse and previously unreported series of heterocyclic and aryl substituted groups (24 examples) and allowing access to all four stereoisomers of these valuable building blocks. PMID:25523503

  13. Asymmetric synthesis of both enantiomers of anti-4,4,4-trifluorothreonine and 2-amino-4,4,4-trifluorobutanoic acid.

    PubMed

    Jiang, Zhong-Xing; Qin, Ying-Ying; Qing, Feng-Ling

    2003-09-19

    A short and efficient enantioselective synthesis of both enantiomers of anti-4,4,4-trifluorothreonine and 2-amino-4,4,4-trifluorobutanoic acid was successfully developed. Trifluoromethylation of benzyl-protected bromoalkene 4 provided key intermediate trifluoromethylated trans-disubstituted alkene 2 in good yield. The sequence then involved Sharpless asymmetric dihydroxylation, nucleophilic opening of cyclic sulfate with NaN(3), palladium-catalyzed selective hydrogenation, and oxidation. PMID:12968918

  14. Palladium-catalyzed intramolecular asymmetric C-H functionalization/cyclization reaction of metallocenes: an efficient approach toward the synthesis of planar chiral metallocene compounds.

    PubMed

    Deng, Ruixian; Huang, Yunze; Ma, Xinna; Li, Gencheng; Zhu, Rui; Wang, Bin; Kang, Yan-Biao; Gu, Zhenhua

    2014-03-26

    A palladium-catalyzed asymmetric synthesis of planar chiral metallocene compounds is reported. The reaction stereoselectively functionalized one of the ortho C-H bonds of Cp rings by intramolecular cyclization to form indenone derivatives in high yields with excellent enantioselectivity. The mild set of reaction conditions allowed a wide variety of chiral metallocene compounds to be synthesized with broad functional group tolerance. The influences of preinstalled chiralities on the other Cp-ring were also investigated. PMID:24617772

  15. Lewis Acid Catalyzed Asymmetric Three-Component Coupling Reaction: Facile Synthesis of ?-Fluoromethylated Tertiary Alcohols.

    PubMed

    Aikawa, Kohsuke; Kondo, Daisuke; Honda, Kazuya; Mikami, Koichi

    2015-12-01

    A chiral dicationic palladium complex is found to be an efficient Lewis acid catalyst for the synthesis of ?-fluoromethyl-substituted tertiary alcohols using a three-component coupling reaction. The reaction transforms three simple and readily available components (terminal alkyne, arene, and fluoromethylpyruvate) to valuable chiral organofluorine compounds. This strategy is completely atom-economical and results in perfect regioselectivities and high enantioselectivities of the corresponding tertiary allylic alcohols in good to excellent yields. PMID:26486488

  16. Asymmetric synthesis from terminal alkenes by diboration/cross-coupling cascades

    PubMed Central

    Mlynarski, Scott N.; Schuster, Christopher H.; Morken, James P.

    2013-01-01

    Amongst prospective starting materials for organic synthesis, terminal (monosubstituted) alkenes are ideal. In the form of ?-olefins, they are manufactured on enormous scale and they are the core product features from many organic chemical reactions. While their latent reactivity can easily enable hydrocarbon chain extension, alkenes also have the attractive feature of being stable in the presence of many acids, bases, oxidants and reductants. In spite of these impressive attributes, relatively few catalytic enantioselective transformations have been developed that transform aliphatic ?-olefins in >90% ee and, with the exception of site-controlled isotactic polymerization of ?-olefins,1 none of these processes result in chain-extending C-C bond formation to the terminal carbon.2, 3, 4, 5, 6 Herein, we describe a strategy that directly addresses this gap in synthetic methodology and present a single-flask catalytic enantioselective conversion of terminal alkenes into a range of chiral products. These reactions are enabled by an unusual neighboring group participation effect that accelerates Pd-catalyzed cross-coupling of 1,2-bis(boronates) relative to nonfunctionalized alkyl boronate analogs. In tandem with enantioselective diboration, this reactivity feature connects abundant alkene starting materials to a diverse array of chiral products. Importantly with respect to synthesis utility, the tandem diboration/cross-coupling reaction (DCC reaction) generally provides products in high yield and high selectivity (>95:5 enantiomer ratio), employs low loadings (1–2 mol %) of commercially available catalysts and reagents, it offers an expansive substrate scope, and can address a broad range of alcohol and amine synthesis targets, many of which cannot be easily addressed with current technology. PMID:24352229

  17. Asymmetric Synthesis of 1,2,9,9a-Tetrahydrocyclopropa[c]benzo[e]indol-4-one (CBI)

    PubMed Central

    Lajiness, James P.; Boger, Dale L.

    2011-01-01

    A short, asymmetric synthesis of the 1,2,9,9a-tetrahydrocyclopropa[c]benzo[e]indol-4-one (CBI) analogue of the CC-1065 and duocarmycin DNA alkylation subunits is described. Treatment of iodo-epoxide 5, prepared by late-stage alkylation of 4 with (S)-glycidal-3-nosylate, with EtMgBr at room temperature directly provides the optically pure alcohol 6 in 87% yield (99% ee) derived from selective metal–halogen exchange and subsequent regioselective intramolecular 6-endo-tet cyclization. The use of MeMgBr or i-PrMgBr also provides the product in high yields (82–87%), but requires larger amounts of the Grignard reagent to effect metal–halogen exchange and cyclization. Direct transannular spirocyclization of 7 following O-debenzylation of 6 provides N-Boc-CBI. This approach represents the most efficient (9-steps, 31% overall) and effective (99% ee) route to the optically pure CBI alkylation subunit yet described. PMID:21192653

  18. Trienamine catalyzed asymmetric synthesis and biological investigation of a cytochalasin B-inspired compound collection.

    PubMed

    Sellstedt, Magnus; Schwalfenberg, Melanie; Ziegler, Slava; Antonchick, Andrey P; Waldmann, Herbert

    2016-01-01

    Due to their enhanced metabolic needs many cancers need a sufficient supply of glucose, and novel inhibitors of glucose import are in high demand. Cytochalasin B (CB) is a potent natural glucose import inhibitor which also impairs the actin cytoskeleton leading to undesired toxicity. With a view to identifying selective glucose import inhibitors we have developed an enantioselective trienamine catalyzed synthesis of a CB-inspired compound collection. Biological analysis revealed that indeed actin impairment can be distinguished from glucose import inhibition and led to the identification of the first selective glucose import inhibitor based on the basic structural architecture of cytochalasin B. PMID:26606903

  19. Protodeboronation of tertiary boronic esters: asymmetric synthesis of tertiary alkyl stereogenic centers.

    PubMed

    Nave, Stefan; Sonawane, Ravindra P; Elford, Tim G; Aggarwal, Varinder K

    2010-12-01

    While tertiary boranes undergo efficient protodeboronation with carboxylic acids, tertiary boronic esters do not. Instead, we have discovered that CsF with 1.1 equiv of H2O (on tertiary diarylalkyl boronic esters) or TBAF·3H2O (on tertiary aryldialkyl boronic esters) effect highly efficient protodeboronation of tertiary boronic esters with essentially complete retention of configuration. Furthermore, substituting D2O for H2O provides ready access to deuterium-labeled enantioenriched tertiary alkanes. The methodology has been applied to a short synthesis of the sesquiterpene, (S)-turmerone. PMID:21080646

  20. Synthesis, Annealing and Performance of Pd-Au Asymmetric Composite Membranes for Hydrogen Purification

    SciTech Connect

    Ma, Yi Hua; Chen, Chao-Huang; Catalano, Jacopo; Guazzone, Federico; Payzant, E Andrew

    2013-01-01

    Composite asymmetric Pd-Au membranes, based on porous Inconel and Hastelloy tubular supports, were prepared by means of electroless deposition and galvanic displacement techniques and tested, before and after Au deposition, in pure H2 atmosphere. The final membranes, with Au average bulk composition up to 16.7 wt%, were 9 15 m thick and showed, for the entire duration of characterization, H2/He ideal selectivity in excess of 900. The annealing of the as-prepared membranes was conducted through the coating and diffusion mechanism in He and H2 atmospheres at 500 C. The annealing conditions were chosen after non-isothermal and isothermal HT-XRD studies on coupons synthetized with similar preparation methods. After the formation of the Pd-Au layer, the membranes showed steady flux and a stable Au gradient on the membrane top layer. Comparisons between permeance for Pd/Au and pure Pd membranes indicated that the membranes with an Au average bulk composition of 4.5 and 5.4 wt% had an enhancement, up to 20%, of the H2 permeability in the temperature range 250 450 C with respect to pure Pd membranes. On the other hand, the membrane having the highest Au composition, 16.7 wt%, even though characterized by a lower H2 permeability (77% of pure Pd) had a rather high surface Au composition (approximately 46 wt%), which might provide good H2S poisoning tolerance.

  1. Enantioselective synthesis of highly functionalized dihydrofurans through copper-catalyzed asymmetric formal [3+2] cycloaddition of ?-ketoesters with propargylic esters.

    PubMed

    Zhu, Fu-Lin; Wang, Ya-Hui; Zhang, De-Yang; Xu, Jie; Hu, Xiang-Ping

    2014-09-15

    An enantioselective synthesis of highly functionalized dihydrofurans through a copper-catalyzed asymmetric [3+2] cycloaddition of ?-ketoesters with propargylic esters has been developed. With a combination of Cu(OTf)2 and a chiral tridentate P,N,N ligand as the catalyst, a variety of 2,3-dihydrofurans bearing an exocyclic double bond at the 2?position were obtained in good chemical yields and with good to high enantioselectivities. The exocyclic double bond can be hydrogenated in a highly diastereoselective fashion to give unusual cis-2,3-dihydrofuran derivatives, thus further enhancing the scope of this transformation. PMID:25088662

  2. Copper-catalyzed asymmetric synthesis and comparative aldose reductase inhibition activity of (+)/(-)-1,2-benzothiazine-1,1-dioxide acetic acid derivatives.

    PubMed

    Parveen, Shagufta; Hussain, Saghir; Qin, Xiangyu; Hao, Xin; Zhu, Shaojuan; Rui, Miao; Zhang, Shuzhen; Fu, Fengyan; Ma, Bing; Yu, Qun; Zhu, Changjin

    2014-06-01

    A copper catalyst system for the asymmetric 1,4-hydrosilylation of the ?,?-unsaturated carboxylate class was developed by which synthesis of (+)- and (-)-enantiomers of 1,2-benzothiazine-1,1-dioxide acetates has been achieved with a good yield and an excellent level of enantioselectivity. A comparative structure-activity relationship study yielded the following order of aldose reductase inhibition activity: (-)-enantiomers > racemic > (+)-enantiomers. Further, a molecular docking study suggested that the (-)-enantiomer had significant binding affinity and thus increased inhibition activity. PMID:24785266

  3. Total Synthesis and Tentative Structural Elucidation of Cryptomoscatone E3: Interplay of Experimental and Computational Studies.

    PubMed

    Novaes, Luiz F T; Sarotti, Ariel M; Pilli, Ronaldo A

    2015-12-18

    A successful combination of computational chemistry and total synthesis was explored to tentatively elucidate the absolute configuration of cryptomoscatone E3, a polyketide isolated from the Brazilian tree Cryptocarya mandiocanna. Two independent synthetic approaches are discussed based on asymmetric allylation, ring closing metathesis, and aldol reactions. PMID:26513545

  4. New chiral phosphinephosphinite ligands: Application to stereoselective synthesis of a key intermediate of 1{beta}-methyl carbapenems by Rh(I)-catalyzed asymmetric hydroformylation

    SciTech Connect

    Saito, Takao; Yoshida, Akifumi; Matsumura, Kazuhiko

    1995-12-31

    Transition metal catalyzed asymmetric hydroformylation is an attractive and highly useful homologation process for organic synthesis. Recently, the authors reported that the Rh(I) complexes of phosphinephosphite BINAPHOS are highly efficient catalysts for enantioselective hydroformylation of a variety of olefins. This time, the authors have designed and synthesized new chiral phosphinephosphinite ligands having binaphthyl backbone, (R)-2-diarylphosphino-2{prime}-diarylphosphinoxy-1,1{prime}-binaphthy1 (hereafter abbreviated (R)-BIPNITE). The Rh(I) complexes of these ligands are effective catalysts for the asymmetric hydroformylation of 4-vinylazetidin-2-one to give the corresponding oxo-aldehyde 3{beta} as the major product in very high diastereoselectivities and in good regioselectivities. Interestingly, modifications of the aryl substituents in phosphine and phosphinite moieties afforded higher selectivities. Aldehyde 3{beta} was easily oxidized with NaClO{sub 2} to 4, a key intermediate of 1{beta}-methyl carbapenems. Thus, the present method provides a new practical route to a versatile key intermediate for the synthesis of carbapenem antibiotics.

  5. An Asymmetric Stereodivergent Strategy Towards Aminocyclitols

    PubMed Central

    Malhotra, Sushant

    2014-01-01

    A concise asymmetric synthesis of aminocyclitols such as diastereomeric 2-deoxystreptamine analogues and conduramine A is described. The Pd-catalyzed asymmetric desymmetrization of meso 1,4-dibenzolate enables the synthesis of highly oxidized cyclohaxane architectures. These scaffolds can potentially be used to access novel aminoglycoside antibiotics and enantiomerically pure ?-glucosidase inhibitors. PMID:24889256

  6. Enantioselective Synthesis of syn-?-Aryl-?-hydroxy Weinreb Amides: Catalytic Asymmetric Roskamp Reaction of ?-Aryl Diazo Weinreb Amides.

    PubMed

    Shin, Sung Ho; Baek, Eun Hee; Hwang, Geum-Sook; Ryu, Do Hyun

    2015-10-01

    A convenient one-pot procedure to synthesize a variety of highly optically active syn-?-aryl-?-hydroxy Weinreb amides using an asymmetric Roskamp/reduction strategy is described. An oxazaborolidinium ion catalyzed asymmetric Roskamp reaction of ?-aryl diazo Weinreb amides with aldehydes produced ?-phenyl-?-keto Weinreb amides, which were in situ reduced with zinc borohydride to give syn-?-aryl-?-hydroxy Weinreb amides in good yields (up to 87%) with high enantioselectivities (up to 99% ee) and syn stereoselectivities (>20:1). PMID:26393875

  7. Application of 3-Methyl-2-vinylindoles in Catalytic Asymmetric Povarov Reaction: Diastereo- and Enantioselective Synthesis of Indole-Derived Tetrahydroquinolines.

    PubMed

    Dai, Wei; Jiang, Xiao-Li; Tao, Ji-Yu; Shi, Feng

    2016-01-01

    The first application of 3-methyl-2-vinylindoles in catalytic asymmetric Povarov reactions has been established via the three-component reactions of 3-methyl-2-vinylindoles, aldehydes, and anilines in the presence of chiral phosphoric acid, providing easy access to chiral indole-derived tetrahydroquinolines with three contiguous stereogenic centers at high yields (up to 99%) and with excellent diastereo- and enantioselectivities (all >95:5 dr, up to 96% ee). This mode of catalytic asymmetric three-component reaction offers a step-economic and atom-economic strategy for accessing enantioenriched indole-derived tetrahydroquinolines with structural diversity and complexity. PMID:26652222

  8. Diastereoselective Allylation of "N"-"Tert"-Butanesulfinyl Imines: An Asymmetric Synthesis Experiment for the Undergraduate Organic Laboratory

    ERIC Educational Resources Information Center

    Chen, Xiao-Yang; Sun, Li-Sen; Gao, Xiang; Sun, Xing-Wen

    2015-01-01

    An asymmetric synthetic experiment that encompasses both diastereoselectivity and enantioselectivity is described. In this experiment, Zn-mediated allylation of an ("R")-"N"-"tert"-butanesulfinyl imine is first performed to obtain either diastereomer using two different solvent systems, followed by oxidation of the…

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

    PubMed

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

    2015-04-01

    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. PMID:25821893

  10. Green synthesis of asymmetrically textured silver meso-flowers (AgMFs) as highly sensitive SERS substrates.

    PubMed

    Nhung, Tran Thi; Lee, Sang-Wha

    2014-12-10

    Highly asymmetrical "flower-like" micron silver particles, so-called hierarchical silver meso-flowers (AgMFs), were facilely synthesized using ascorbic acid at room temperature in the presence of chitosan biopolymer. The time-evolution of TEM images and XRD analysis confirmed the anisotropic growth of AgMFs with single crystalline phase of which the formation mechanism was described in detail. The morphology and size of as-prepared AgMFs were tunable simply by changing the concentration of chitosan biopolymer and/or AgNO3 precursor under otherwise identical conditions. The asymmetrically textured AgMFs dramatically enhanced Raman signals of probe molecules (2-chlorothiophenol, 4-aminothiophenol) even at a single particle level because of their surface morphologies consisting of numerous nanoedges and crevices. PMID:25369521

  11. Crystallography of magnetite plaquettes and their significance as asymmetric catalysts for the synthesis of chiral organics in carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Chan, Q. H. S.; Zolensky, M. E.

    2015-10-01

    We have previously observed the magnetite plaquettes in carbonaceous chondrites using scanning electron microscope (SEM) imaging, examined the crystal orientation of the polished surfaces of magnetite plaquettes in CI Orgueil using electron backscattered diffraction (EBSD) analysis, and concluded that these magnetite plaquettes are likely naturally asymmetric materials [1]. In this study, we expanded our EBSD observation to other magnetite plaquettes in Orgueil, and further examined the internal structure of these remarkable crystals with the use of X-ray computed microtomography.

  12. Crystallography of Magnetite Plaquettes and their Significance as Asymmetric Catalysts for the Synthesis of Chiral Organics in Carbonaceous Chondrites

    NASA Technical Reports Server (NTRS)

    Chan, Q. H. S.; Zolensky, M. E.

    2015-01-01

    We have previously observed the magnetite plaquettes in carbonaceous chondrites using scanning electron microscope (SEM) imaging, examined the crystal orientation of the polished surfaces of magnetite plaquettes in CI Orgueil using electron backscattered diffraction (EBSD) analysis, and concluded that these magnetite plaquettes are likely naturally asymmetric materials. In this study, we expanded our EBSD observation to other magnetite plaquettes in Orgueil, and further examined the internal structure of these remarkable crystals with the use of X-ray computed microtomography.

  13. Stereoselective synthesis of multisubstituted alkenes via ring opening reactions of cyclopropenes. Enantioselective copper catalysed asymmetric reduction of alkenylheteroarenes. 

    E-print Network

    Wang, Yi

    2010-01-01

    A catalytic organometallic addition-ring opening sequence of cyclopropenes that enables the efficient and highly stereoselective synthesis of multisubstituted alkenes has been developed. A possible mechanism of organoaluminium reaction is proposed...

  14. A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

    PubMed Central

    Denmark, Scott E.; Gould, Nathan D.; Wolf, Larry M.

    2011-01-01

    Despite over three decades of research into asymmetric phase transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with a libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity oriented approach wherein the tandem inter[4+2]/intra[3+2] cycloaddition of nitroalkenes serves as the key transformation. A two part synthetic strategy comprised of: (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way based on the effective positive potential of the ammonium ion. PMID:21446721

  15. One-step synthesis of graphene nanoribbon-MnO2 hybrids and their all-solid-state asymmetric supercapacitors

    NASA Astrophysics Data System (ADS)

    Liu, Mingkai; Tjiu, Weng Weei; Pan, Jisheng; Zhang, Chao; Gao, Wei; Liu, Tianxi

    2014-03-01

    Three-dimensional (3D) hierarchical hybrid nanomaterials (GNR-MnO2) of graphene nanoribbons (GNR) and MnO2 nanoparticles have been prepared via a one-step method. GNR, with unique features such as high aspect ratio and plane integrity, has been obtained by longitudinal unzipping of multi-walled carbon nanotubes (CNTs). By tuning the amount of oxidant used, different mass loadings of MnO2 nanoparticles have been uniformly deposited on the surface of GNRs. Asymmetric supercapacitors have been fabricated with the GNR-MnO2 hybrid as the positive electrode and GNR sheets as the negative electrode. Due to the desirable porous structure, excellent electrical conductivity, as well as high rate capability and specific capacitances of both the GNR and GNR-MnO2 hybrid, the optimized GNR//GNR-MnO2 asymmetric supercapacitor can be cycled reversibly in an enlarged potential window of 0-2.0 V. In addition, the fabricated GNR//GNR-MnO2 asymmetric supercapacitor exhibits a significantly enhanced maximum energy density of 29.4 W h kg-1 (at a power density of 12.1 kW kg-1), compared with that of the symmetric cells based on GNR-MnO2 hybrids or GNR sheets. This greatly enhanced energy storage ability and high rate capability can be attributed to the homogeneous dispersion and excellent pseudocapacitive performance of MnO2 nanoparticles and the high electrical conductivity of the GNRs.Three-dimensional (3D) hierarchical hybrid nanomaterials (GNR-MnO2) of graphene nanoribbons (GNR) and MnO2 nanoparticles have been prepared via a one-step method. GNR, with unique features such as high aspect ratio and plane integrity, has been obtained by longitudinal unzipping of multi-walled carbon nanotubes (CNTs). By tuning the amount of oxidant used, different mass loadings of MnO2 nanoparticles have been uniformly deposited on the surface of GNRs. Asymmetric supercapacitors have been fabricated with the GNR-MnO2 hybrid as the positive electrode and GNR sheets as the negative electrode. Due to the desirable porous structure, excellent electrical conductivity, as well as high rate capability and specific capacitances of both the GNR and GNR-MnO2 hybrid, the optimized GNR//GNR-MnO2 asymmetric supercapacitor can be cycled reversibly in an enlarged potential window of 0-2.0 V. In addition, the fabricated GNR//GNR-MnO2 asymmetric supercapacitor exhibits a significantly enhanced maximum energy density of 29.4 W h kg-1 (at a power density of 12.1 kW kg-1), compared with that of the symmetric cells based on GNR-MnO2 hybrids or GNR sheets. This greatly enhanced energy storage ability and high rate capability can be attributed to the homogeneous dispersion and excellent pseudocapacitive performance of MnO2 nanoparticles and the high electrical conductivity of the GNRs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06650a

  16. Asymmetric synthesis of 2,3-dihydropyrroles by ring-opening/cyclization of cyclopropyl ketones using primary amines.

    PubMed

    Xia, Yong; Liu, Xiaohua; Zheng, Haifeng; Lin, Lili; Feng, Xiaoming

    2015-01-01

    The asymmetric ring-opening/cyclization of cyclopropyl ketones with primary amine nucleophiles was catalyzed by a chiral N,N'-dioxide/scandium(III) complex through a kinetic resolution process. A broad range of cyclopropyl ketones and primary amines are suitable substrates of this reaction. The corresponding products were afforded in excellent enantioselectivities and yields (up to 97?%?ee and 98?% yield) under mild reaction conditions. This method provides a promising access to chiral 2,3-dihydropyrroles as well as an effective procedure for the kinetic resolution of 2-substituted cyclopropyl ketones. PMID:25363459

  17. Concise diastereoselective synthesis of calcaripeptide C via asymmetric transfer hydrogenation/Pd-induced chiral allenylzinc as a key reaction.

    PubMed

    Kumaraswamy, Gullapalli; Narayanarao, Vykunthapu; Raju, Ragam

    2015-08-21

    Synthesis of the natural product calcaripeptide C derived from the fungal metabolite mycelium KF525 of Calcarisporium sp. has been achieved. This complementary approach avoids the use of a stoichiometric amount of chiral auxiliary reagents as commonly used to generate enantioenriched advanced precursors. The enantioselective synthesis of calcaripeptide C is remarkable in that using catalytic reactions sets the two stereogenic centers efficiently with good levels of enantioselectivity. Further diversification of the calcaripeptide C structures is possible by employing a complementary catalytic enantioenriched Ru-catalyst. PMID:26156428

  18. Absolute optical instruments without spherical symmetry

    NASA Astrophysics Data System (ADS)

    Tyc, Tomáš; Dao, H. L.; Danner, Aaron J.

    2015-11-01

    Until now, the known set of absolute optical instruments has been limited to those containing high levels of symmetry. Here, we demonstrate a method of mathematically constructing refractive index profiles that result in asymmetric absolute optical instruments. The method is based on the analogy between geometrical optics and classical mechanics and employs Lagrangians that separate in Cartesian coordinates. In addition, our method can be used to construct the index profiles of most previously known absolute optical instruments, as well as infinitely many different ones.

  19. Acylation, Diastereoselective Alkylation, and Cleavage of an Oxazolidinone Chiral Auxiliary: A Multistep Asymmetric Synthesis Experiment for Advanced Undergraduates

    ERIC Educational Resources Information Center

    Smith, Thomas E.; Richardson, David P.; Truran, George A.; Belecki, Katherine; Onishi, Megumi

    2008-01-01

    An introduction to the concepts and experimental techniques of diastereoselective synthesis using a chiral auxiliary is described. The 4-benzyl-2-oxazolidinone chiral auxiliary developed by Evans is acylated with propionic anhydride under mild conditions using DMAP as an acyl transfer catalyst. Deprotonation with NaN(TMS)[subscript 2] at -78…

  20. Asymmetric synthesis of allylic sulfonic acids: enantio- and regioselective iridium-catalyzed allylations of Na2SO3.

    PubMed

    Liu, Wei; Zhao, Xiao-ming; Zhang, Hong-bo; Zhang, Liang; Zhao, Ming-zhu

    2014-12-15

    An enantioselective allylation reaction of allylic carbonates with sodium sulfite (Na2 SO3 ) catalyzed by Ir complex was accomplished, providing allylic sulfonic acids in good to excellent yields with a high level of enantio- and regioselectivities. (R)-2-Phenyl-2-sulfoacetic acid, a key intermediate for the synthesis of Cefsulodin and Sulbenicillin, was synthesized as well. PMID:25367779

  1. Brucine diol-copper-catalyzed asymmetric synthesis of endo-pyrrolidines: the mechanistic dichotomy of imino esters.

    PubMed

    Li, Jian-Yuan; Kim, Hun Young; Oh, Kyungsoo

    2015-03-01

    Enantio- and diastereodivergent approaches to pyrrolidines are described by using catalyst- and substrate-controlled reaction pathways. A concerted endo-selective [3 + 2]-cycloaddition pathway is developed for the reaction of methyl imino ester, whereas endo-pyrrolidines with an opposite absolute stereochemical outcome are prepared by using the stepwise reaction pathway of tert-butyl imino ester. The development of catalyst- and substrate-controlled stereodivergent approaches highlights the inherent substrate-catalyst interactions in the [3 + 2]-cycloaddition reactions of metalated azomethine ylides. PMID:25695534

  2. A new method for the synthesis of ?-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues

    PubMed Central

    Mazurkiewicz, Roman; Grymel, Miros?awa; Zieli?ska, Katarzyna; Adamek, Jakub; Chmielewska, Ewa; Bochno, Marta; Kubica, Sonia

    2015-01-01

    Summary A convenient approach has been developed to ?-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues by ?-phosphonylation, ?-phosphinylation or ?-phosphinoylation of 1-(N-acylamino)alkylphosphonates, that, in turn, are easily accessible from N-acyl-?-amino acids. Effective electrophilic activation of the ?-position of 1-(N-acetylamino)alkylphosphonates was achieved by electrochemical ?-methoxylation of these compounds in methanol, mediated with NaCl, followed by displacement of the methoxy group with triphenylphosphonium tetrafluoroborate to give hitherto unknown 1-(N-acetylamino)-1-triphenylphosphoniumalkylphosphonate tetrafluoroborates. The latter compounds react smoothly with trialkyl phosphites, dialkyl phosphonites or alkyl phosphinites in the presence of Hünig’s base and methyltriphenylphosphonium iodide in a Michaelis–Arbuzov-like reaction to give the expected alkylidenebisphosphonates, 1-phosphinylalkylphosphonates or 1-phosphinoylalkylphosphonates, respectively, in good yields. PMID:26425197

  3. Configurationally Stable, Enantioenriched Organometallic Nucleophiles in Stereospecific Pd-Catalyzed Cross-Coupling Reactions: An Alternative Approach to Asymmetric Synthesis

    PubMed Central

    Wang, Chao-Yuan; Derosaa, Joseph

    2015-01-01

    Several research groups have recently developed methods to employ configurationally stable, enantioenriched organometallic nucleophiles in stereospecific Pd-catalyzed cross-coupling reactions. By establishing the absolute configuration of a chiral alkyltin or alkylboron nucleophile prior to its use in cross-coupling reactions, new stereogenic centers may be rapidly and reliably generated with preservation of the known initial stereochemistry. While this area of research is still in its infancy, such stereospecific cross-coupling reactions may emerge as simple, general methods to access diverse, optically active products from common enantioenriched organometallic building blocks. This minireview highlights recent progress towards the development of general, stereospecific Pd-catalyzed cross-coupling reactions using configurationally stable organometallic nucleophiles. PMID:26388985

  4. Synthesis of Silyloxy Dienes by Silylene Tranfer to Divinyl Ketones: Application to the Asymmetric Sythesis of Substituted Cyclohexanes

    PubMed Central

    Ventocilla, Christian C.; Woerpel, K. A.

    2012-01-01

    Silver-catalyzed silylene transfer to divinyl ketones provided 2-silyloxy-1,3-dienes with control of stereochemistry and regioselectivity. The products participated in Diels–Alder reactions with electron-deficient alkenes and imines to form six-membered ring products diastereoselectively. Cycloaddition reactions with alkenes bearing chiral auxiliaries provided access to chiral, non-racemic cyclohexenes. The methodology therefore represents a synthesis of diastereomerically and enantiomerically pure products in a single flask. The highly substituted cyclohexene products could be functionalized stereoselectively to provide cyclohexanols after oxidation of the carbon–silicon bond. PMID:22372733

  5. Asymmetric One-Pot Synthesis of 1,3-Oxazolidines and 1,3-Oxazinanes via Hemiaminal Intermediates

    PubMed Central

    2015-01-01

    A highly efficient method for the enantioselective one-pot synthesis of 1,3-oxazolidines and 1,3-oxazinanes has been reported. The reaction proceeds via the formation of hemiaminal intermediates obtained by the enantioselective addition of respective alcohols to imines catalyzed by a chiral magnesium phosphate catalyst, followed by intramolecular cyclization under mildly basic conditions. A wide range of substrates have been converted to the respective chiral heterocyclic products in high yields and with excellent enantioselectivities using this one-pot procedure. PMID:25075467

  6. An approach to catalytic asymmetric electrocyclization

    E-print Network

    Kothari, Abhishek

    2010-02-09

    Chapter 1 outlines the development of a catalytic electrocyclic process and its exploitation in asymmetric synthesis. Since Woodward and Hoffmann delineated a rationale for the mechanism and stereochemistry of these reactions they have become...

  7. Catalytic asymmetric sulfenylation to structurally diverse dithioketals.

    PubMed

    Liao, Kui; Zhou, Feng; Yu, Jin-Sheng; Gao, Wei-Ming; Zhou, Jian

    2015-10-29

    We report the first example of the highly enantioselective synthesis of structurally diverse chiral dithioketals via asymmetric sulfenylation of various types of S-based nucleophiles, catalyzed by a cheap cinchona alkaloid derivative, dihydroquinine. PMID:26399606

  8. Synthesis and characterization of mesoporous spinel NiCo2O4 using surfactant-assembled dispersion for asymmetric supercapacitors

    NASA Astrophysics Data System (ADS)

    Hsu, Chun-Tsung; Hu, Chi-Chang

    2013-11-01

    A simple and scalable process has been developed for synthesizing spinel NiCo2O4 nanocrystals through a thermal decomposition method. The introduction of hexadecyltrimethylammonium bromide (CTAB, (C16H33)N(CH3)3Br) into precursor solutions significantly enhances the homogeneity and porosity of spinel NiCo2O4. The porosity and high specific surface area of NiCo2O4 preserves the brilliant pseudo-capacitive performances due to providing smooth paths for electrolyte penetration and ion diffusion into inner active sites. Morphologies and microstructures of the active materials are examined by transmission electron microscopic (TEM) and X-ray diffraction (XRD) analyses. Thermogravimetric analysis (TGA) is used to evaluate the thermal properties of precursor solutions. The electrochemical performances of NiCo2O4 are systematically characterized by cyclic voltammetry and charge-discharge tests. Asymmetric supercapacitors are assembled with these brilliant binary oxides as the positive electrode and activated carbon as the negative electrode. The highly porous NiCo2O4 exhibits superior capacitive performances, i.e., high specific capacitance (764 F g-1 at 2 mV s-1) and long cycle life.

  9. PEG mediated synthesis and biological evaluation of asymmetrical pyrazole curcumin analogues as potential analgesic, anti-inflammatory and antioxidant agents.

    PubMed

    Jadhav, Shravan Y; Bhosale, Raghunath B; Shirame, Sachin P; Patil, Sandeep B; Kulkarni, Suresh D

    2015-03-01

    The new series of asymmetrical pyrazole curcumin analogues 4a-g were synthesized by using polyethylene glycol (PEG-400) as a green reaction medium and evaluated for their in vivo analgesic and in vitro antioxidant (H2 O2 , DPPH, Ferrous reducing power and Nitric oxide scavenging activity) and anti-inflammatory activities. All the compounds synthesized 4a-g showed the potential to demonstrate analgesic activity as compared to the standard ibuprofen. Among the tested series, compounds 4e and 4b exhibited good hydrogen peroxide scavenging activity as compared to the standard butylated hydroxy toluene (BHT). Compounds 4b, 4d, 4f, and 4g showed good DPPH free radical scavenging activity. Compounds 4b, 4c, 4d, 4e and 4g showed excellent ferrous-reducing power activity, whereas all the compounds showed better nitric oxide scavenging activity than standard ascorbic acid. Additionally, all the synthesized compounds were also screened for their in vitro anti-inflammatory activity. Compounds 4b, 4d, 4f and 4g showed good anti-inflammatory activity as compared to standard diclofenac sodium. PMID:25130070

  10. 1: Mass asymmetric fission barriers for {sup 98}Mo; 2: Synthesis and characterization of actinide-specific chelating agents

    SciTech Connect

    Veeck, A.C.

    1996-08-01

    Excitation functions have been measured for complex fragment emission from the compound nucleus {sup 98}Mo, produced by the reaction of {sup 86}Kr with {sup 12}C. Mass asymmetric fission barriers have been obtained by fitting the excitation functions with a transition state formalism. The extracted barriers are {approximately} 5.7 MeV higher, on average, than the calculations of the Rotating Finite Range Model (RFRM). These data clearly show an isospin dependence of the conditional barriers when compared with the extracted barriers from {sup 90}Mo and {sup 94}Mo. Eleven different liquid/liquid extractants were synthesized based upon the chelating moieties 3,2-HOPO and 3,4-HOPO; additionally, two liquid/liquid extractants based upon the 1,2-HOPO chelating moiety were obtained for extraction studies. The Pu(IV) extractions, quite surprisingly, yielded results that were very different from the Fe(III) extractions. The first trend remained the same: the 1,2-HOPOs were the best extractants, followed closely by the 3,2-HOPOs, followed by the 3,4-HOPOs; but in these Pu(IV) extractions the 3,4-HOPOs performed much better than in the Fe(III) extractions. 129 refs.

  11. Synthesis and thermotropic properties of novel double-chained quaternary ammonium chlorides with symmetric and asymmetric hydrocarbon chain length

    NASA Astrophysics Data System (ADS)

    Ding, Zhaoyun; Hao, Aiyou

    2009-04-01

    A series of novel double-chained quaternary ammonium chlorides with symmetrical and asymmetrical hydrocarbon chain length R 1-O-CH 2-CH(OH)-CH 2-N +(CH 3) 2-R 2·Cl - (R 1, R 2: C 12H 25, C 14H 29, C 16H 33) have been synthesized by the reaction of 1- O-alkyl glycidyl ether with N, N-dimethylalkylamine and N, N-dimethylalkylamine hydrochloride. Their chemical structures have been characterized through FT-IR, 1H NMR, MS and elementary analysis. Their thermotropic properties have been examined by differential scanning calorimetry (DSC), polarizing light microscopy (PLM) and X-ray diffraction (XRD). It has been found that the compounds with longer hydrocarbon chain length and being higher asymmetry in hydrocarbon chain length exhibit lower melting point ( Tm) , isotropization temperature ( Ti) and narrower mesophase temperature range. However, the hydrocarbon chain length and the symmetry in the hydrocarbon chain length have little influence on the type of liquid crystals. All compounds form cholesteric liquid crystal.

  12. Teaching Absolute Value Meaningfully

    ERIC Educational Resources Information Center

    Wade, Angela

    2012-01-01

    What is the meaning of absolute value? And why do teachers teach students how to solve absolute value equations? Absolute value is a concept introduced in first-year algebra and then reinforced in later courses. Various authors have suggested instructional methods for teaching absolute value to high school students (Wei 2005; Stallings-Roberts…

  13. Synthesis and determination of the absolute configuration of Armatol A through a polyepoxide cyclization cascade : revision of the proposed structures of Armatols A-F

    E-print Network

    Underwood, Brian Saxton

    2011-01-01

    Cyclization Cascades Leading to the Tricyclic Fragment of Armatol A The synthesis of the fused 6,7,7-tricycle of armatol A was investigated. Fragments containing both a ketone and an aldehyde for subsequent fragment coupling ...

  14. The Origin of Remarkable Chromatographic Differences in Novel Azulenyl-1,5-diols; & Synthesis and Use of Phosphinine and Phosphabarrelene Ligands for Asymmetric Catalysis

    NASA Astrophysics Data System (ADS)

    Horgen, Dana Ann

    The synthesis, characterization and analysis of novel chiral molecules advance many areas of synthetic organic chemistry, both industrially and academically. This work touches on three of the major methods for obtaining enantiomerically pure compounds. Based on the observation of a remarkably large difference in the silica TLC mobility of a pair of azulene 1,5-diol diastereomers, a series of such azulene 1,5-diols were prepared. Every pair of diastereomers was especially well separated, and X-ray crystallography revealed a conformational explanation of the large differences in mobility. The separation of the diol enantiomers was then studied on two chiral HLPC columns. The enantiomers were well-resolved, the separation appearing to benefit from the presence of the azulene ring. In addition, the more polar diastereomers on silica TLC gave dramatically better enantiomer separations on a Chiralcel-OD-H column. Very few chiral phosphinine and phosphabarrelene ligands have been reported in the literature but have shown promise as good ligands for asymmetric catalysis. Our group had previously synthesized a C2-symmetric chiral bis-camphorphosphinine and the derived bis-camphorphosphabarrelene but neither had been tested as ligands for hydroformylation. In this work, optimization of the synthesis of these two compounds was undertaken. In addition, modifications to the structure of these molecules that incorporated electron donating (N,N-dimethylaminophenyl-) or electron withdrawing (trifluoromethyl-) substituents were made in an attempt to affect the electronic nature of the phosphorus atom. Steric modifications were also done to create a more hindered environment around the phosphorus atom. The activity and selectivity of bis-camphorphosphinine, bis-camphorphosphabarrelene and other chiral phosphinine molecules serving as ligands in the rhodiumcatalyzed hydroformylation of styrene were compared to other phosphorus ligands recently published in the literature. All of these ligands gave complexes that have moderate activity with good regioselectivity but very little enantioselectivity. Therefore, more tuning of these ligands' properties need to be done in order to achieve the activity and selectivity of other chiral monodentate-ligands. The bis-camphorphosphabarrelene was also a successful organocatalyst of the Baylis-Hillman reaction, showing its versatility in both metal-catalyzed and metal-free catalysis.

  15. Applications of organocatalytic asymmetric synthesis to drug prototypes--dual action and selective inhibitors of n-nitric oxide synthase with activity against the 5-HT1D/1B subreceptors.

    PubMed

    Hanessian, Stephen; Stoffman, Eli; Mi, Xueling; Renton, Paul

    2011-03-01

    The scope of MacMillan's organocatalytic asymmetric conjugate addition reaction of indoles and electron-rich aromatics to ?,?-unsaturated aldehydes has been extended to the use of 3-amino crotonaldehydes as substrates. The aromatics used include indoles as well as an aniline and a furan. The scope and effect of the groups on nitrogen (R, R') has also been studied. The method has been applied to the concise synthesis of an advanced precursor to S-(+)-1, a drug prototype for the treatment of migraine headaches. PMID:21271688

  16. Absolute nuclear material assay

    DOEpatents

    Prasad, Manoj K. (Pleasanton, CA); Snyderman, Neal J. (Berkeley, CA); Rowland, Mark S. (Alamo, CA)

    2010-07-13

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  17. Absolute nuclear material assay

    DOEpatents

    Prasad, Manoj K. (Pleasanton, CA); Snyderman, Neal J. (Berkeley, CA); Rowland, Mark S. (Alamo, CA)

    2012-05-15

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  18. Synthesis, Crystal Structure, Absolute Configuration and Antitumor Activity of the Enantiomers of 5-Bromo-2-chloro-N-(1-phenylethyl)pyridine-3-sulfonamide.

    PubMed

    Zhou, Zhixu; Li, Linwei; Yan, Ning; Du, Lei; Sun, Changshan; Sun, Tiemin

    2015-01-01

    Pyridinesulfonamide is an important fragment which has a wide range of applications in novel drugs. R- and S-isomers of 5-bromo-2-chloro-N-(1-phenylethyl)pyridine-3-sulfonamide have been synthesized, and the stereostructures have been researched. Single crystals of both compounds were obtained for X-ray analysis, and the absolute configurations (ACs) have been further confirmed by electronic circular dichroism (ECD), optical rotation (OR) and quantum chemical calculations. The crystal structures and calculated geometries were extremely similar, which permitted a comparison of the relative reliabilities of ACs obtained by ECD analyses and theoretical simulation. In addition, the effect of stereochemistry on the PI3K? kinase and anticancer activity were investigated. Compounds 10a and 10b inhibit the activity of PI3K? kinase with IC50 values of 1.08 and 2.69 ?M, respectively. Furthermore, molecular docking was performed to analyze the binding modes of R- and S-isomers. PMID:26610458

  19. Asymmetric Total Synthesis of Spongistatins 1 and 2 Michael T. Crimmins,* Jason D. Katz, David G. Washburn, Shawn P. Allwein, and Laura F. McAtee

    E-print Network

    benzyl ether of alkene 10 was reductively cleaved to deliver alcohol 11, which was subjected to a two irradiation,14 followed by Swern oxidation of the resultant alcohol gave the aldehyde 7. Asymmetric aldol provided the alcohol 8 (96:4 d.r.) after reductive removal of the auxiliary. Selective protection

  20. An absolute Johnson noise thermometer

    E-print Network

    Luca Callegaro; Vincenzo D'Elia; Marco Pisani; Alessio Pollarolo

    2009-01-30

    We developed an absolute Johnson noise thermometer (JNT), an instrument to measure the thermodynamic temperature of a sensing resistor, with traceability to voltage, resistance and frequency quantities. The temperature is measured in energy units, and can be converted to SI units (kelvin) with the accepted value of the Boltzmann constant kb; or, conversely, it can be employed to perform measurements at the triple point of water, and obtain a determination of kb. The thermometer is composed of a correlation spectrum analyzer an a calibrated noise source, both constructed around commercial mixed-signal boards. The calibrator generates a pseudorandom noise, by digital synthesis and amplitude scaling with inductive voltage dividers; the signal spectrum is a frequency comb covering the measurement bandwidth. JNT measurements at room temperature are compatible with those of a standard platinum resistance thermometer within the combined uncertainty of 60 ppm. A path towards future improvements of JNT accuracy is also sketched.

  1. Asymmetric Redox-Annulation of Cyclic Amines

    PubMed Central

    2015-01-01

    Cyclic amines such as 1,2,3,4-tetrahydroisoquinoline undergo regiodivergent annulation reactions with 4-nitrobutyraldehydes. These redox-neutral transformations enable the asymmetric synthesis of highly substituted polycyclic ring systems in just two steps from commercial materials. The utility of this process is illustrated in a rapid synthesis of (?)-protoemetinol. Computational studies provide mechanistic insights and implicate the elimination of acetic acid from an ammonium nitronate intermediate as the rate-determining step. PMID:26348653

  2. Asymmetric fluorocyclizations of alkenes.

    PubMed

    Wolstenhulme, Jamie R; Gouverneur, Véronique

    2014-12-16

    CONSPECTUS: The vicinal fluorofunctionalization of alkenes is an attractive transformation that converts feedstock olefins into valuable cyclic fluorinated molecules for application in the pharmaceutical, agrochemical, medical, and material sectors. The challenges associated with asymmetric fluorocyclizations induced by F(+) reagents are distinct from other types of halocyclizations. Processes initiated by the addition of an F(+) reagent onto an alkene do not involve the reversible formation of bridged fluoronium ions but generate acyclic ?-fluorocationic intermediates. This mechanistic feature implies that fluorocyclizations are not stereospecific. A discontinuity exists between the importance of this class of fluorocyclization and the activation modes currently available to implement successful catalysis. Progress toward fluorocyclization has been achieved by investing in neutral and cationic [NF] reagent development. The body of work on asymmetric fluorination using chiral cationic [NF](+) reagents prepared by fluorine transfer from the dicationic [NF](2+) reagent Selectfluor to quinuclidines, inspired the development of asymmetric F(+)-induced fluorocyclizations catalyzed by cinchona alkaloids; for catalysis, the use of N-fluorobenzenesulfonimide, which is less reactive than Selectfluor, ensures that the achiral F(+) source remains unreactive toward the alkene. These organocatalyzed enantioselective fluorocyclizations can be applied to indoles to install the fluorine on a quaternary benzylic stereogenic carbon center and to afford fluorinated analogues of natural products featuring the hexahydropyrrolo[2,3-b]indole or the tetrahydro-2H-furo[2,3-b]indole skeleton. In an alternative approach, the poor solubility of dicationic Selectfluor bis(tetrafluoroborate) in nonpolar solvent was exploited with anionic phase transfer catalysis as the operating activation mode. Exchange of the tetrafluoroborate ions of Selectfluor with bulky lipophilic chiral anions (e.g., TRIP and derivatives) brings into solution the resulting chiral Selectfluor reagent, now capable of asymmetric fluorocyclization. This strategy is best applied to a subset of substrates bearing a nucleophilic pendent group (benzamide is best) capable of hydrogen bonding for association with the chiral phosphate catalyst. These contributions focused on fluoroheterocyclization involving either O- or N-nucleophiles. As for other halocyclizations, alkenes armed with ? C-nucleophiles represent the most demanding class of substrates for asymmetric F(+)-induced electrophilic fluorination-cyclization. Successful implementation required the design of new chiral Selectfluor reagents featuring stereogenicity on the DABCO core. These reagents, accessible from chiral vicinal diamines, allowed the synthesis of unusual chiral fluorine-containing tetracyclic compounds, some composed of carbon, hydrogen, and fluorine exclusively. The challenges associated with F(+)-induced fluorocarbocyclizations prompted methodologists to consider chemistry where the Csp(3)-F bond formation event follows a catalyst-controlled cyclization. An exciting development built on in the area of transition metal ?-cyclization of polyenes leading to cationic metal-alkyl intermediates. When intercepted by oxidative fluorodemetalation with a F(+) source, the resulting products are complex polycyclic structures emerging from an overall catalytic cascade fluorocarbocyclization. Complementing F(+)-based reactions, examples of fluorocyclizations with fluoride in the presence of an oxidant were reported. Despite some exciting developments, the field of asymmetric fluorocyclizations is in its infancy and undoubtedly requires new activation modes, catalysts, as well as F(+) and F(-) reagents to progress into general retrosynthetic approach toward enantioenriched fluorocycles. Numerous opportunities emerge, not least the use of a latent fluorine source as a means to minimize background fluorination. PMID:25379791

  3. Improved synthesis and application of planar-chiral nucleophilic catalysts in asymmetric reactions and copper-catalyzed enantioselective N-H insertion reactions

    E-print Network

    Lee, Elaine C

    2007-01-01

    The development of an improved synthesis of nucleophilic planar-chiral catalysts is described in Chapter 1. This route is amenable to scale-up and preparative chiral HPLC is unnecessary to resolve the racemic catalysts. ...

  4. Cinchona Alkaloid Squaramide-Catalyzed Asymmetric Michael Addition of ?-Aryl Isocyanoacetates to ?-Trifluoromethylated Enones and Its Applications in the Synthesis of Chiral ?-Trifluoromethylated Pyrrolines.

    PubMed

    Zhao, Mei-Xin; Zhu, Hui-Kai; Dai, Tong-Lei; Shi, Min

    2015-11-20

    Cinchona alkaloid squaramide can effectively catalyze the asymmetric Michael addition of ?-aryl isocyanoacetates to ?-trifluoromethylated enones, affording the corresponding adducts with an adjacent chiral tertiary carbon center bearing a CF3 group and a quaternary carbon center in moderate to good yields along with excellent stereoselectivities. The adduct can be easily transformed into biologically attractive chiral ?-trifluoromethylated pyrroline carboxylate in high yield via an isocyano group hydrolysis/cyclization/dehydration cascade reaction by treating with acid. The one-pot enantioselective Michael addition/isocyano group hydrolysis/cyclization/dehydration sequential protocol has also been investigated. PMID:26523421

  5. Catalytic Asymmetric Hydrogenation PhospholaneOxazoline Ligands for Ir-Catalyzed

    E-print Network

    Zhang, Xumu

    Section Representative experimental procedure: VO(OiPr)3 (5 mL, 20 mmol) and hydroxamic acid (26.6 mg, 60 of functionalized alkenes, see: a) R. A. Johnson, K. B. Sharpless in Catalytic Asymmetric Synthesis, 2nd ed. (Ed.: I. Jörgensen, Chem. Rev. 1989, 89, 431; c) T. Katsuki in Catalytic Asymmetric Synthesis, 2nd ed. (Ed.: I. Ojima

  6. Asymmetric Ashes

    NASA Astrophysics Data System (ADS)

    2006-11-01

    Astronomers are reporting remarkable new findings that shed light on a decade-long debate about one kind of supernovae, the explosions that mark a star's final demise: does the star die in a slow burn or with a fast bang? From their observations, the scientists find that the matter ejected by the explosion shows significant peripheral asymmetry but a nearly spherical interior, most likely implying that the explosion finally propagates at supersonic speed. These results are reported today in Science Express, the online version of the research journal Science, by Lifan Wang, Texas A&M University (USA), and colleagues Dietrich Baade and Ferdinando Patat from ESO. "Our results strongly suggest a two-stage explosion process in this type of supernova," comments Wang. "This is an important finding with potential implications in cosmology." ESO PR Photo 44/06 ESO PR Photo 44/06 Clumpy Explosion (Artist's Impression) Using observations of 17 supernovae made over more than 10 years with ESO's Very Large Telescope and the McDonald Observatory's Otto Struve Telescope, astronomers inferred the shape and structure of the debris cloud thrown out from Type Ia supernovae. Such supernovae are thought to be the result of the explosion of a small and dense star - a white dwarf - inside a binary system. As its companion continuously spills matter onto the white dwarf, the white dwarf reaches a critical mass, leading to a fatal instability and the supernova. But what sparks the initial explosion, and how the blast travels through the star have long been thorny issues. The supernovae Wang and his colleagues observed occurred in distant galaxies, and because of the vast cosmic distances could not be studied in detail using conventional imaging techniques, including interferometry. Instead, the team determined the shape of the exploding cocoons by recording the polarisation of the light from the dying stars. Polarimetry relies on the fact that light is composed of electromagnetic waves that oscillate in certain directions. Reflection or scattering of light favours certain orientations of the electric and magnetic fields over others. This is why polarising sunglasses can filter out the glint of sunlight reflected off a pond. When light scatters through the expanding debris of a supernova, it retains information about the orientation of the scattering layers. If the supernova is spherically symmetric, all orientations will be present equally and will average out, so there will be no net polarisation. If, however, the gas shell is not round, a slight net polarisation will be imprinted on the light. This is what broad-band polarimetry can accomplish. If additional spectral information is available ('spectro-polarimetry'), one can determine whether the asymmetry is in the continuum light or in some spectral lines. In the case of the Type Ia supernovae, the astronomers found that the continuum polarisation is very small so that the overall shape of the explosion is crudely spherical. But the much larger polarization in strongly blue-shifted spectral lines evidences the presence, in the outer regions, of fast moving clumps with peculiar chemical composition. "Our study reveals that explosions of Type Ia supernovae are really three-dimensional phenomena," says Dietrich Baade. "The outer regions of the blast cloud is asymmetric, with different materials found in 'clumps', while the inner regions are smooth." "This study was possible because polarimetry could unfold its full strength thanks to the light-collecting power of the Very Large Telescope and the very precise calibration of the FORS instrument," he adds. The research team first spotted this asymmetry in 2003, as part of the same observational campaign (ESO PR 23/03 and ESO PR Photo 26/05). The new, more extensive results show that the degree of polarisation and, hence, the asphericity, correlates with the intrinsic brightness of the explosion. The brighter the supernova, the smoother, or less clumpy, it is. "This has some impact on the us

  7. Divergent total synthesis of the Lycopodium alkaloids huperzine A, huperzine B, and huperzine U.

    PubMed

    Ding, Rui; Fu, Jian-Guo; Xu, Guang-Qiang; Sun, Bing-Feng; Lin, Guo-Qiang

    2014-01-01

    Huperzine A, huperzine B, and huperzine U are congeners isolated from the Chinese herb Huperzia serrata (= Lycopodium serratum ) in minuscule amounts. The most efficient total synthesis of huperzine A, the first asymmetric total syntheses of huperzine B, and the first total synthesis of huperzine U have been achieved efficiently in overall yields of 17%, 10%, and 9%, respectively, each spanning 10-13 steps from (R)-pulegone. The featured steps include palladium-catalyzed Buchwald-Hartwig coupling and Heck cyclization reactions and an Ir-catalyzed olefin isomerization reaction. This work has established the absolute configurations of huperzine B and huperzine U and revealed that natural huperzine A, huperzine B, and huperzine U possess the same set of absolute stereochemistries, thus providing support for the potential role of huperzine B and huperzine U in the biosynthesis of huperzine A. PMID:24299147

  8. Computing Solar Absolute Fluxes

    E-print Network

    Carlos Allende Prieto

    2007-09-14

    Computed color indices and spectral shapes for individual stars are routinely compared with observations for essentially all spectral types, but absolute fluxes are rarely tested. We can confront observed irradiances with the predictions from model atmospheres for a few stars with accurate angular diameter measurements, notably the Sun. Previous calculations have been hampered by inconsistencies and the use of outdated atomic data and abundances. I provide here a progress report on our current efforts to compute absolute fluxes for solar model photospheres. Uncertainties in the solar composition constitute a significant source of error in computing solar radiative fluxes.

  9. The absolute path command

    Energy Science and Technology Software Center (ESTSC)

    2012-05-11

    The ap command traveres all symlinks in a given file, directory, or executable name to identify the final absolute path. It can print just the final path, each intermediate link along with the symlink chan, and the permissions and ownership of each directory component in the final path. It has functionality similar to "which", except that it shows the final path instead of the first path. It is also similar to "pwd", but it canmore »provide the absolute path to a relative directory from the current working directory.« less

  10. Tunable synthesis of hierarchical NiCo2O4 nanosheets-decorated Cu/CuOx nanowires architectures for asymmetric electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Kuang, Min; Zhang, Yu Xin; Li, Tong Tao; Li, Kai Feng; Zhang, Sheng Mao; Li, Gang; Zhang, Wei

    2015-06-01

    We demonstrate a facile and tunable preparative strategy of porous NiCo2O4 nanosheets-decorated Cu-based nanowires hybrids as high-performance supercapacitor electrodes. A fast faradic reaction has been realized by inducing elementary copper core in the composite, which assists in high electric conductivity of the cell and creates intimate channels for fast charge collection and electron transfer. As a result, this hybrid composite electrode displays high specific capacitance (578 F g-1 at current density of 1.0 A g-1) and rate capability (80.1% capacitance retention from 1 A g-1 to 10 A g-1). Additionally, asymmetric device is constructed from NiCo2O4/Cu-based NWs and activated graphene (AG) with an operation potential from 0 to 1.4 V. The asymmetric device exhibits an energy density of 12.6 Wh kg-1 at a power density of 344 W kg-1 and excellent long-term cycling stability (only 1.8% loss of its initial capacitance after 10,000 cycles). These attractive findings suggest that such unique NiCo2O4/Cu-based NWs hybrid architecture is promising for electrochemical applications as efficient electrode material.

  11. Asymmetric Dark Matter

    E-print Network

    Jason Kumar

    2013-09-17

    We review the theoretical framework underlying models of asymmetric dark matter, describe astrophysical constraints which arise from observations of neutron stars, and discuss the prospects for detecting asymmetric dark matter.

  12. Asymmetric dark matter

    SciTech Connect

    Kumar, Jason

    2014-06-24

    We review the theoretical framework underlying models of asymmetric dark matter, describe astrophysical constraints which arise from observations of neutron stars, and discuss the prospects for detecting asymmetric dark matter.

  13. Symmetric Cryptography Asymmetric Cryptography

    E-print Network

    Ramkumar, Mahalingam

    Outline Trust Symmetric Cryptography Asymmetric Cryptography Key Management Network Security Cryptography - A Review Mahalingam Ramkumar Mississippi State University, MS September 22, 2006 Ramkumar Review #12;Outline Trust Symmetric Cryptography Asymmetric Cryptography Key Management Network Security 1

  14. Symmetric Cryptography Asymmetric Cryptography

    E-print Network

    Ramkumar, Mahalingam

    Outline Symmetric Cryptography Asymmetric Cryptography Key Management Network Security Cryptography Symmetric Cryptography Asymmetric Cryptography Key Management Network Security 1 Symmetric Cryptography Symmetric Cryptography Overview Block Cipher Modes Multiple Encryption Hash Functions Message Authentication

  15. Total synthesis of Class II and Class III Galbulimima Alkaloids

    E-print Network

    Tjandra, Meiliana

    2010-01-01

    I. Total Synthesis of All Class III Galbulimima Alkaloids We describe the total synthesis of (+)- and (-)-galbulimima alkaloid 13, (-)-himgaline anad (-)-himbadine. The absolute stereochemistry of natural (-)-galbulimima ...

  16. Efficient synthesis of optically pure alcohols by asymmetric hydrogen-transfer biocatalysis: application of engineered enzymes in a 2-propanol-water medium.

    PubMed

    Itoh, Nobuya; Isotani, Kentaro; Nakamura, Masatoshi; Inoue, Kousuke; Isogai, Yasuhiro; Makino, Yoshihide

    2012-02-01

    We describe an efficient method for producing both enantiomers of chiral alcohols by asymmetric hydrogen-transfer bioreduction of ketones in a 2-propanol (IPA)-water medium with E. coli biocatalysts expressing phenylacetaldehyde reductase (PAR: wild-type and mutant enzymes) from Rhodococcus sp. ST-10 and alcohol dehydrogenase from Leifsonia sp. S749 (LSADH). We also describe the detailed properties of mutant PARs, Sar268, and HAR1, which were engineered to have high activity and productivity in media composed of polar organic solvent and water, and the construction of three-dimensional structure of PAR by homology modeling. The K(m) and V(max) values for some substrates and the substrate specificity of mutant PARs were quite different from those of wild-type PAR. The results well explained the increased productivity of engineered PARs in IPA-water medium. PMID:21739266

  17. Zn(II), Ni(II), Cu(II) and Pb(II) complexes of tridentate asymmetrical Schiff base ligands: Synthesis, characterization, properties and biological activity

    NASA Astrophysics Data System (ADS)

    ?ahin, Mustafa; Koçak, Nuriye; Erdenay, Damla; Arslan, U?ur

    2013-02-01

    New asymmetrical tridentate Schiff base ligands were synthesized using 1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-hydroxy-1-napthaldehyde, 9-anthracenecarboxaldehyde. Schiff base ligands and their metal complexes were synthesised and characterized by using FT-IR, 1H NMR, 13C NMR, UV-Vis, XRD, ESR, elemental analysis and fluorescence studies. The antimicrobial activity of the ligands and their metal complexes were studied against Staphylococcus aureus ATCC 29213, S. aureus ATCC 25923, Streptococcus mutans RSHM 676, Enterococcus faecalis ATCC 29212, Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853. The determination of the antibacterial activity was done using the broth microdilution methods. In general, it has been determined that the studied compounds have MIC values similar to Gram-positive and Gram-negative bacteria. It has been found that Ni, Pb, Zn derivatives of HL1A and ZnL2A has lower MIC values than ampicillin for P. aeruginosa ATCC 27853 strain.

  18. Controlled synthesis, asymmetrical transport behavior and luminescence properties of lanthanide doped ZnO mushroom-like 3D hierarchical structures

    NASA Astrophysics Data System (ADS)

    Yue, Dan; Lu, Wei; Jin, Lin; Li, Chunyang; Luo, Wen; Wang, Mengnan; Wang, Zhenling; Hao, Jianhua

    2014-10-01

    Lanthanide doped ZnO mushroom-like 3D hierarchical structures have been fabricated by polyol-mediated method and characterized by various microstructural and optical techniques. The results indicate that the as-prepared ZnO:Ln3+ (Ln = Tb, Eu) samples have a hexagonal phase structure and possess a mushroom-like 3D hierarchical morphology. The length of the whole mushroom from stipe bottom to pileus top is about 1.0 ?m, and the diameters of pileus and stipe are about 0.8 ?m and 0.4 ?m, respectively. It is found that the flow of N2 is the key parameter for the formation of the novel ZnO structure and the addition of (NH4)2HPO4 has a prominent effect on the phase structure and the growth of mushroom-like morphology. The potential mechanism of forming this morphology is proposed. The pileus of the formed mushroom is assembled by several radial ZnO:Ln3+ nanorods, whereas the stipe is composed of over layered ZnO:Ln3+ nanosheets. Moreover, asymmetrical I-V characteristic curves of ZnO:Ln3+ mushrooms indicate that the texture composition of the 3D hierarchical morphology might lead to the asymmetrical transport behavior of electrical conductivity. Lanthanide doped ZnO samples can exhibit red or green emission under the excitation of UV light.Lanthanide doped ZnO mushroom-like 3D hierarchical structures have been fabricated by polyol-mediated method and characterized by various microstructural and optical techniques. The results indicate that the as-prepared ZnO:Ln3+ (Ln = Tb, Eu) samples have a hexagonal phase structure and possess a mushroom-like 3D hierarchical morphology. The length of the whole mushroom from stipe bottom to pileus top is about 1.0 ?m, and the diameters of pileus and stipe are about 0.8 ?m and 0.4 ?m, respectively. It is found that the flow of N2 is the key parameter for the formation of the novel ZnO structure and the addition of (NH4)2HPO4 has a prominent effect on the phase structure and the growth of mushroom-like morphology. The potential mechanism of forming this morphology is proposed. The pileus of the formed mushroom is assembled by several radial ZnO:Ln3+ nanorods, whereas the stipe is composed of over layered ZnO:Ln3+ nanosheets. Moreover, asymmetrical I-V characteristic curves of ZnO:Ln3+ mushrooms indicate that the texture composition of the 3D hierarchical morphology might lead to the asymmetrical transport behavior of electrical conductivity. Lanthanide doped ZnO samples can exhibit red or green emission under the excitation of UV light. Electronic supplementary information (ESI) available: STEM-SEI image and EDS elemental mapping of an individual ZnO: Eu3+ mushroom. See DOI: 10.1039/c4nr04359f

  19. Solvothermal Synthesis of Three-Dimensional Hierarchical CuS Microspheres from a Cu-Based Ionic Liquid Precursor for High-Performance Asymmetric Supercapacitors.

    PubMed

    Zhang, Jing; Feng, Huijie; Yang, Jiaqin; Qin, Qing; Fan, Hongmin; Wei, Caiying; Zheng, Wenjun

    2015-10-01

    It is meaningful to exploit copper sulfide materials with desired structure as well as potential application due to their cheapness and low toxicity. A low-temperature and facile solvothermal method for preparing three-dimensional (3D) hierarchical covellite (CuS) microspheres from an ionic liquid precursor [Bmim]2Cu2Cl6 (Bmim = 1-butyl-3-methylimidazolium) is reported. The formation of CuS nanostructures was achieved by decomposition of intermediate complex Cu(Tu)3Cl (thiourea = Tu), which produced CuS microspheres with diameters of 2.5-4 ?m assembled by nanosheets with thicknesses of 10-15 nm. The ionic liquid, as an "all-in-one" medium, played a key role for the fabrication and self-assembly of CuS nanosheets. The alkylimidazolium rings ([Bmim](+)) were found to adsorb onto the (001) facets of CuS crystals, which inhibited the crystal growth along the [001] direction, while the alkyl chain had influence on the assembly of CuS nanosheets. The CuS microspheres showed enhanced electrochemical performance and high stability for the application in supercapacitors due to intriguing structural design and large specific surface area. When this well-defined CuS electrode was assembled into an asymmetric supercapacitor (ASC) with an activated carbon (AC) electrode, the CuS//AC-ASC demonstrated good cycle performance (?88% capacitance after 4000 cycles) and high energy density (15.06 W h kg(-1) at a power density of 392.9 W kg(-1)). This work provides new insights into the use of copper sulfide electrode materials for asymmetric supercapacitors and other electrochemical devices. PMID:26371955

  20. Absolute configuration of neostenine

    NASA Astrophysics Data System (ADS)

    Jiang, Ren-Wang; Ye, Wencai; Shaw, Pang-Chui; But, Paul Pui-Hay; Mak, Thomas C. W.

    2010-03-01

    Heavy atoms bromine and iodine were incorporated into the neostenine ( 1) skeleton through reductive cleavage of the lactone ring, followed by acylation with 4-bromobenzoyl chloride, and salt formation with methyl iodide, respectively. The absolute configuration of the seven chiral centers C1, C9, C9a, C10, C11, C1 and C13 in 1 were assigned as S, S, R, R, R, R, and S, respectively, based on the Flack parameters in X-ray structure refinement, and results from the two heavy atom derivatives are consistent with each other. As many Stemona alkaloids share the same lactone and pyrrolo[1,2-?]azepine nucleus as those in 1, the facile method reported in this paper can be applied for the determination of absolute configurations of similar alkaloids.

  1. New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones

    PubMed Central

    2012-01-01

    Enantioselective hydrogenation of ketones is a key reaction in organic chemistry. In the past, we have attempted to deal with some unsolved challenges in this arena by introducing chiral tridentate phosphine-diamine/Ru catalysts. New catalysts and new applications are presented here, including the synthesis of phosphine-amino-alcohol P,N,OH ligands derived from (R,S)-1-amino-2-indanol, (S,S)-1-amino-2-indanol and a new chiral P,N,N ligand derived from (R,R)-1,2-diphenylethylenediamine. Ruthenium pre-catalysts of type [RuCl2(L)(DMSO)] were isolated and then examined in the hydrogenation of ketones. While the new P,N,OH ligand based catalysts are poor, the new P,N,N system gives up to 98% e.e. on substrates that do not react at all with most catalysts. A preliminary attempt at realising a new delta lactone synthesis by organocatalytic Michael addition between acetophenone and acrylonitrile, followed by asymmetric hydrogenation of the nitrile functionalised ketone is challenging in part due to the Michael addition chemistry, but also since Noyori pressure hydrogenation catalysts gave massively reduced reactivity relative to their performance for other acetophenone derivatives. The Ru phosphine-diamine system allowed quantitative conversion and around 50% e.e. The product can be converted into a delta lactone by treatment with KOH with complete retention of enantiomeric excess. This approach potentially offers access to this class of chiral molecules in three steps from the extremely cheap building blocks acrylonitrile and methyl-ketones; we encourage researchers to improve on our efforts in this potentially useful but currently flawed process. PMID:23216944

  2. Pacific trench motions controlled by the asymmetric plate configuration

    E-print Network

    Buck, Roger

    Pacific trench motions controlled by the asymmetric plate configuration Thorsten J. Nagel,1 William; accepted 29 February 2008; published 23 May 2008. [1] We present a novel explanation for absolute trench of a simple finite difference scheme to estimate the effect on trench motion velocities. The hypothesis

  3. Spontaneous resolution, asymmetric catalysis, and fluorescence properties of ?- and ?-[cu(tzmp)]N enantiomers from in situ [2 + 3] cycloaddition synthesis.

    PubMed

    Tang, Yun-Zhi; Xiong, Jian-Bo; Gao, Ji-Xing; Tan, Yu-Hui; Xu, Qing; Wen, He-Rui

    2015-06-01

    Although a number of acentric or chiral tetrazole complexes were synthesized from Sharpless reaction, there are no spontaneous resolution Cu(I)-tetrazole compounds from in situ [2 + 3] cycloaddition synthesis that have been reported before. The first enantiomers ?- and ?- of metal tetrazole compound [Cu(Tzmp)]n (1) (HTzmp = 3-tetrazolemethylpyridine) were obtained and isolated from in situ [2 + 3] cycloaddition reactions of a flexible organic nitrile (3-cyanomethylpyridine) with sodium azide in the presence of CuCl2 as the Lewis acid. ?-1 and ?-1 feature a homochiral helical coordination polymeric system and {4(4).6(2)} two-dimensional framework. The photoluminescence study suggests 1 exhibits strong green fluorescence in solid state with maximal emission peaks around 535 nm. Remarkably, the ?- and ?- of [Cu(Tzmp)]n (1) catalyzes the enantioselective Henry reaction with high yield (more than 96%) and certain enantioselectivity (up to 69%). PMID:25970815

  4. The information as Absolute

    E-print Network

    Sergey V. Shevchenko; Vladimir V. Tokarevsky

    2013-03-11

    This article presents and grounds (i.e. presents proof of the existence, the truth, the self-consistence and the completeness of)the informational conception ("the Information as Absolute" conception)in physics and philosophy. the conception defines the information as an ultimately common, real and fundamental concept/phenomenon - "Absolute", which exists as anabsolutely infinite set ("Information" Set) of elements (members) and informational (e.g., logical) linksbetween the elements; where any element itself is some informational structure also. Correspondingly, for example, Matter as the substence, radiation, etc., is some development or realization of informational patterns, constituting a specific - and practically infinitesimal comparing to the Set - subset of the "Information" Set. The conception allows for the resolution, or at least for a consideration on a higher level of comprehension, of the basic ontological and epistemological problems in philosophy and natural sciences; in physics it allows to suggest reasonable model, which makes more clear basic phisical notions,such as space, time, matter, etc.

  5. Synthesis, spectroscopic characterization and antimicrobial activity of binuclear metal complexes of a new asymmetrical Schiff base ligand: DNA binding affinity of copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Shebl, Magdy

    2014-01-01

    The 1:1 condensation of o-acetoacetylphenol and 1,2-diaminopropane under condition of high dilution gives the mono-condensed Schiff base, (E)-3-(1-aminopropan-2-ylimino)-1-(2-hydroxyphenyl)butan-1-one. The mono-condensed Schiff base has been used for further condensation with isatin to obtain the new asymmetrical dicompartmental Schiff base ligand, (E)-3-(2-((E)-4-(2-hydroxyphenyl)-4-oxobutan-2-ylideneamino) propylimino)indolin-2-one (H3L) with a N2O3 donor set. Reactions of the ligand with metal salts give a series of new binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, 1H and 13C NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. The analytical and spectroscopic tools showed that the complexes can be formulated as: [(HL)(VO)2(SO4)(H2O)]·4H2O, [(HL)Fe2Cl4(H2O)3]·EtOH, [(HL)Fe2(ox)Cl2(H2O)3]·2H2O, [(L)M2(OAc)(H2O)m]·nH2O; M = Co, Ni or Cu, m = 4, 0 and n = 2, 3, [(HL)Cu2Cl]Cl·6H2O and [(L)(UO2)2(OAc)(H2O)3]·6H2O. The metal complexes exhibited octahedral geometrical arrangements except copper complexes that exhibited tetrahedral geometries and uranyl complex in which the metal ion is octa-coordinated. The Schiff base and its metal complexes were evaluated for antimicrobial activity against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli) and fungi (Candida albicans and Aspergillus flavus). The ligand and some of its complexes were found to be biologically active. The DNA-binding properties of the copper complexes (6 and 7) have been investigated by electronic absorption, fluorescence and viscosity measurements. The results obtained indicate that these complexes bind to DNA via an intercalation binding mode with an intrinsic binding constant, Kb of 1.34 × 104 and 2.5 × 104 M-1, respectively.

  6. Asymmetric transformations of achiral 2,5-cyclohexadienones

    PubMed Central

    Kalstabakken, Kyle A.; Harned, Andrew M.

    2014-01-01

    Cyclohexadienones are versatile platforms for performing asymmetric synthesis as evidenced by the numerous natural product syntheses that exploit their diverse reactivity profile. However, there are few general methods available for the direct asymmetric synthesis of chiral cyclohexadienones. To circumvent this problem, several researchers have developed catalytic asymmetric methods that employ readily available achiral 2,5-cyclohexadienones as substrates. Many of these reactions are desymmetrizations in which one of the enantiotopic alkenes of an achiral dienone is transformed. Others involve selective reaction at one alkene of an unsymmetrically substituted, achiral dienone. This review will cover advances in this area over the last 20 years and the application of these strategies in complex molecule synthesis. PMID:26688596

  7. Asymmetric Black Diholes

    SciTech Connect

    Manko, V. S.; Sanchez-Mondragon, J.; Ruiz, E.

    2009-05-01

    In the present paper we enlarge the list of black dihole spacetimes by introducing the notion of asymmetric black diholes which describe configurations composed of two static charged black holes endowed with unequal masses and equal but opposite charges. The asymmetric dihole solutions are considered both in the Einstein-Maxwell and Einstein-Maxwell-dilaton theories.

  8. January 2004 Asymmetric Cell

    E-print Network

    Extavour, Cassandra

    January 2004 Asymmetric Cell Division By Pamela J. Hines and Suzanne Kadereit Asymmetric cell cell" is one of the fates. In the case of the stem cell, the cell's first step must be to divide and to produce one daughter like itself, able to continue as a stem cell, and one daughter unlike itself, able

  9. Absolute Equilibrium Entropy

    NASA Technical Reports Server (NTRS)

    Shebalin, John V.

    1997-01-01

    The entropy associated with absolute equilibrium ensemble theories of ideal, homogeneous, fluid and magneto-fluid turbulence is discussed and the three-dimensional fluid case is examined in detail. A sigma-function is defined, whose minimum value with respect to global parameters is the entropy. A comparison is made between the use of global functions sigma and phase functions H (associated with the development of various H-theorems of ideal turbulence). It is shown that the two approaches are complimentary though conceptually different: H-theorems show that an isolated system tends to equilibrium while sigma-functions allow the demonstration that entropy never decreases when two previously isolated systems are combined. This provides a more complete picture of entropy in the statistical mechanics of ideal fluids.

  10. Measurement of the absolute \

    SciTech Connect

    Aunion, Jose Luis Alcaraz; /Barcelona, IFAE

    2010-07-01

    This thesis presents the measurement of the charged current quasi-elastic (CCQE) neutrino-nucleon cross section at neutrino energies around 1 GeV. This measurement has two main physical motivations. On one hand, the neutrino-nucleon interactions at few GeV is a region where existing old data are sparse and with low statistics. The current measurement populates low energy regions with higher statistics and precision than previous experiments. On the other hand, the CCQE interaction is the most useful interaction in neutrino oscillation experiments. The CCQE channel is used to measure the initial and final neutrino fluxes in order to determine the neutrino fraction that disappeared. The neutrino oscillation experiments work at low neutrino energies, so precise measurement of CCQE interactions are essential for flux measurements. The main goal of this thesis is to measure the CCQE absolute neutrino cross section from the SciBooNE data. The SciBar Booster Neutrino Experiment (SciBooNE) is a neutrino and anti-neutrino scattering off experiment. The neutrino energy spectrum works at energies around 1 GeV. SciBooNE was running from June 8th 2007 to August 18th 2008. In that period, the experiment collected a total of 2.65 x 10{sup 20} protons on target (POT). This thesis has used full data collection in neutrino mode 0.99 x 10{sup 20} POT. A CCQE selection cut has been performed, achieving around 70% pure CCQE sample. A fit method has been exclusively developed to determine the absolute CCQE cross section, presenting results in a neutrino energy range from 0.2 to 2 GeV. The results are compatible with the NEUT predictions. The SciBooNE measurement has been compared with both Carbon (MiniBoonE) and deuterium (ANL and BNL) target experiments, showing a good agreement in both cases.

  11. Total synthesis of (+)-iresin.

    PubMed

    Wang, Bian-Lin; Gao, Hai-Tao; Li, Wei-Dong Z

    2015-05-15

    The first asymmetric total synthesis of (+)-iresin (4), an historically important ent-Drimane sesquiterpene lactone, was realized from aldehyde 3 via cyclic orthoester 6 in 5 steps. Notable transformations in this synthesis include a tandem trifluoroperacetic acid (TFPAA)-mediated Baeyer-Villiger oxidation-olefin epoxidation-epoxy ester cyclization, regioselective Burgess dehydration, and regioselective Fétizon oxidative lactonization. PMID:25906145

  12. Generic approach for synthesizing asymmetric nanoparticles and nanoassemblies

    DOEpatents

    Sun, Yugang; Hu, Yongxing

    2015-05-26

    A generic route for synthesis of asymmetric nanostructures. This approach utilizes submicron magnetic particles (Fe.sub.3O.sub.4--SiO.sub.2) as recyclable solid substrates for the assembly of asymmetric nanostructures and purification of the final product. Importantly, an additional SiO.sub.2 layer is employed as a mediation layer to allow for selective modification of target nanoparticles. The partially patched nanoparticles are used as building blocks for different kinds of complex asymmetric nanostructures that cannot be fabricated by conventional approaches. The potential applications such as ultra-sensitive substrates for surface enhanced Raman scattering (SERS) have been included.

  13. The Absolute Relativity Theory

    E-print Network

    Jean-Marc Oury; Bruno Heintz

    2009-08-18

    This paper is a first presentation of a new approach of physics that we propose to refer as the Absolute Relativity Theory (ART) since it refutes the idea of a pre-existing space-time. It includes an algebraic definition of particles, interactions and Lagrangians. It proposed also a purely algebraic explanation of the passing of time phenomenon that leads to see usual Euler-Lagrange equations as the continuous version of the Knizhnik-Zamolodchikov monodromy. The identification of this monodromy with the local ones of the Lorentzian manifolds gives the Einstein equation algebraically explained in a quantized context. A fact that could lead to the unification of physics. By giving an algebraic classification of particles and interactions, the ART also proposes a new branch of physics, namely the Mass Quantification Theory, that provides a general method to calculate the characteristics of particles and interactions. Some examples are provided. The MQT also predicts the existence of as of today not yet observed particles that could be part of the dark matter. By giving a new interpretation of the weak interaction, it also suggests an interpretation of the so-called dark energy.

  14. Absolute Identification by Relative Judgment

    ERIC Educational Resources Information Center

    Stewart, Neil; Brown, Gordon D. A.; Chater, Nick

    2005-01-01

    In unidimensional absolute identification tasks, participants identify stimuli that vary along a single dimension. Performance is surprisingly poor compared with discrimination of the same stimuli. Existing models assume that identification is achieved using long-term representations of absolute magnitudes. The authors propose an alternative…

  15. Asymmetric dark matter stars

    NASA Astrophysics Data System (ADS)

    Kouvaris, Chris; Nielsen, Niklas Grønlund

    2015-09-01

    We study the possibility of asymmetric dark matter with self-interactions forming compact stable objects. We solve the Tolman-Oppenheimer-Volkoff equation and find the mass-radius relation of such "dark stars," their density profile and their Chandrasekhar mass limit. We consider fermionic asymmetric dark matter with Yukawa-type self-interactions appropriate for solving the well-known problems of the collisionless dark matter paradigm. We find that in several cases the relativistic effects are significant.

  16. Asymmetric Dark Matter Stars

    E-print Network

    Kouvaris, Chris

    2015-01-01

    We study the possibility of asymmetric dark matter with self-interactions forming compact stable objects. We solve the Tolman-Oppenheimer-Volkoff equation and find the mass-radius relation of such "dark stars", their density profile and their Chandrasekhar mass limit. We consider fermionic asymmetric dark matter with Yukawa-type self-interactions appropriate for solving the well known problems of the collisionless dark matter paradigm. We find that in several cases the relativistic effects are significant.

  17. Synthesis and Stereochemical Assignment of Crypto-Optically Active (2) H6 -Neopentane.

    PubMed

    Masarwa, Ahmad; Gerbig, Dennis; Oskar, Liron; Loewenstein, Aharon; Reisenauer, Hans Peter; Lesot, Philippe; Schreiner, Peter R; Marek, Ilan

    2015-10-26

    The determination of the absolute configuration of chiral molecules is at the heart of asymmetric synthesis. Here we probe the spectroscopic limits for chiral discrimination with NMR spectroscopy in chiral aligned media and with vibrational circular dichroism spectroscopy of the sixfold-deuterated chiral neopentane. The study of this compound presents formidable challenges since its stereogenicity is only due to small mass differences. For this purpose, we selectively prepared both enantiomers of (2) H6 -1 through a concise synthesis utilizing multifunctional intermediates. While NMR spectroscopy in chiral aligned media could be used to characterize the precursors to (2) H6 -1, the final assignment could only be accomplished with VCD spectroscopy, despite the fleetingly small dichroic properties of 1. Both enantiomers were assigned by matching the VCD spectra with those computed with density functional theory. PMID:26480341

  18. Cryogenic, Absolute, High Pressure Sensor

    NASA Technical Reports Server (NTRS)

    Chapman, John J. (Inventor); Shams. Qamar A. (Inventor); Powers, William T. (Inventor)

    2001-01-01

    A pressure sensor is provided for cryogenic, high pressure applications. A highly doped silicon piezoresistive pressure sensor is bonded to a silicon substrate in an absolute pressure sensing configuration. The absolute pressure sensor is bonded to an aluminum nitride substrate. Aluminum nitride has appropriate coefficient of thermal expansion for use with highly doped silicon at cryogenic temperatures. A group of sensors, either two sensors on two substrates or four sensors on a single substrate are packaged in a pressure vessel.

  19. Asymmetrical field emitter

    DOEpatents

    Fleming, James G. (Albuquerque, NM); Smith, Bradley K. (Albuquerque, NM)

    1995-01-01

    Providing a field emitter with an asymmetrical emitter structure having a very sharp tip in close proximity to its gate. One preferred embodiment of the present invention includes an asymmetrical emitter and a gate. The emitter having a tip and a side is coupled to a substrate. The gate is connected to a step in the substrate. The step has a top surface and a side wall that is substantially parallel to the side of the emitter. The tip of the emitter is in close proximity to the gate. The emitter is at an emitter potential, and the gate is at a gate potential such that with the two potentials at appropriate values, electrons are emitted from the emitter. In one embodiment, the gate is separated from the emitter by an oxide layer, and the emitter is etched anisotropically to form its tip and its asymmetrical structure.

  20. Absolute measurement of cerebral optical coefficients, hemoglobin

    E-print Network

    Fantini, Sergio

    Absolute measurement of cerebral optical coefficients, hemoglobin concentration and oxygen Aron M. Troen Sergio Fantini #12;Absolute measurement of cerebral optical coefficients, hemoglobin-infrared spectroscopy measurement of absolute cerebral hemoglobin concentration and saturation in a large sample of 36

  1. Asymmetric ion trap

    DOEpatents

    Barlow, Stephan E. (Richland, WA); Alexander, Michael L. (Richland, WA); Follansbee, James C. (Pasco, WA)

    1997-01-01

    An ion trap having two end cap electrodes disposed asymmetrically about a center of a ring electrode. The inner surface of the end cap electrodes are conformed to an asymmetric pair of equipotential lines of the harmonic formed by the application of voltages to the electrodes. The asymmetry of the end cap electrodes allows ejection of charged species through the closer of the two electrodes which in turn allows for simultaneously detecting anions and cations expelled from the ion trap through the use of two detectors charged with opposite polarity.

  2. Asymmetric ion trap

    DOEpatents

    Barlow, S.E.; Alexander, M.L.; Follansbee, J.C.

    1997-12-02

    An ion trap having two end cap electrodes disposed asymmetrically about a center of a ring electrode is disclosed. The inner surface of the end cap electrodes are conformed to an asymmetric pair of equipotential lines of the harmonic formed by the application of voltages to the electrodes. The asymmetry of the end cap electrodes allows ejection of charged species through the closer of the two electrodes which in turn allows for simultaneously detecting anions and cations expelled from the ion trap through the use of two detectors charged with opposite polarity. 4 figs.

  3. Absolute instability in a TWT

    NASA Astrophysics Data System (ADS)

    Lau, Y. Y.; Ang, L. K.

    1998-11-01

    There is renewed interest in the traveling wave tube (TWT) because of the recent advances in microwave power module (D. R. Whaley et al., IEEE Trans. Plasma Sci. 26, 912 (1998)) and of the significant growth in satellite communication. A serious threat to the operation of TWT is bandedge oscillation, occurring at the ?-mode of the slow wave circuit. A candidate for bandedge oscillation is the excitation of absolute instability. In this paper, we approximate the circuit mode by a parabola in the dispersion diagram (?-k plane). We use the Briggs-Bers criterion to determine the threshold value of C (C = Pierce parameter) for the onset of absolute instability. The stabilizing effect of a distributed resistive loss, and of velocity detune, is included. The differences in absolute instabilities between fast wave and slow wave devices are discussed.

  4. Absolute transition probabilities of phosphorus.

    NASA Technical Reports Server (NTRS)

    Miller, M. H.; Roig, R. A.; Bengtson, R. D.

    1971-01-01

    Use of a gas-driven shock tube to measure the absolute strengths of 21 P I lines and 126 P II lines (from 3300 to 6900 A). Accuracy for prominent, isolated neutral and ionic lines is estimated to be 28 to 40% and 18 to 30%, respectively. The data and the corresponding theoretical predictions are examined for conformity with the sum rules.-

  5. Asymmetric multiscale detrended fluctuation analysis of California electricity spot price

    NASA Astrophysics Data System (ADS)

    Fan, Qingju

    2016-01-01

    In this paper, we develop a new method called asymmetric multiscale detrended fluctuation analysis, which is an extension of asymmetric detrended fluctuation analysis (A-DFA) and can assess the asymmetry correlation properties of series with a variable scale range. We investigate the asymmetric correlations in California 1999-2000 power market after filtering some periodic trends by empirical mode decomposition (EMD). Our findings show the coexistence of symmetric and asymmetric correlations in the price series of 1999 and strong asymmetric correlations in 2000. What is more, we detect subtle correlation properties of the upward and downward price series for most larger scale intervals in 2000. Meanwhile, the fluctuations of ??(s) (asymmetry) and | ??(s) | (absolute asymmetry) are more significant in 2000 than that in 1999 for larger scale intervals, and they have similar characteristics for smaller scale intervals. We conclude that the strong asymmetry property and different correlation properties of upward and downward price series for larger scale intervals in 2000 have important implications on the collapse of California power market, and our findings shed a new light on the underlying mechanisms of power price.

  6. Multipartite asymmetric quantum cloning

    SciTech Connect

    Iblisdir, S.; Gisin, N.; Acin, A.; Cerf, N.J.; Filip, R.; Fiurasek, J.

    2005-10-15

    We investigate the optimal distribution of quantum information over multipartite systems in asymmetric settings. We introduce cloning transformations that take N identical replicas of a pure state in any dimension as input and yield a collection of clones with nonidentical fidelities. As an example, if the clones are partitioned into a set of M{sub A} clones with fidelity F{sup A} and another set of M{sub B} clones with fidelity F{sup B}, the trade-off between these fidelities is analyzed, and particular cases of optimal N{yields}M{sub A}+M{sub B} cloning machines are exhibited. We also present an optimal 1{yields}1+1+1 cloning machine, which is an example of a tripartite fully asymmetric cloner. Finally, it is shown how these cloning machines can be optically realized.

  7. Cylindrically asymmetric hydrodynamic equations

    E-print Network

    Mikolaj Chojnacki

    2006-09-20

    We show that the boost-invariant and cylindrically asymmetric hydrodynamic equations for baryon-free matter may be rewritten as only two coupled partial differential equations. In the case where the system exhibits the cross-over phase transition, the standard numerical methods may be applied to solve these equations. An example of our results describing non-central gold on gold collisions at RHIC energies is presented.

  8. Asymmetric dipolar ring

    DOEpatents

    Prosandeev, Sergey A. (Fayetteville, AR); Ponomareva, Inna V. (Tampa, FL); Kornev, Igor A. (Ill-de-France, FR); Bellaiche, Laurent M. (Fayetteville, AR)

    2010-11-16

    A device having a dipolar ring surrounding an interior region that is disposed asymmetrically on the ring. The dipolar ring generates a toroidal moment switchable between at least two stable states by a homogeneous field applied to the dipolar ring in the plane of the ring. The ring may be made of ferroelectric or magnetic material. In the former case, the homogeneous field is an electric field and in the latter case, the homogeneous field is a magnetic field.

  9. Asymmetrical Quantum Cryptographic Algorithm

    E-print Network

    Guihua Zeng; Carlos Saavedra; Christoph H. Keitel

    2002-02-04

    A cryptographic algorithm is proposed based on fully quantum mechanical keys and ciphers. Encryption and decryption are carried out via an appropriate measurement process on entangled states as governed by a quantum mechanical, asymmetrical and dynamical public key distribution. The use of public keys leads to a high availability of our scheme, while their quantum nature is shown to ensure unconditional security of the proposed algorithm.

  10. Asymmetric Evolutionary Games.

    PubMed

    McAvoy, Alex; Hauert, Christoph

    2015-08-01

    Evolutionary game theory is a powerful framework for studying evolution in populations of interacting individuals. A common assumption in evolutionary game theory is that interactions are symmetric, which means that the players are distinguished by only their strategies. In nature, however, the microscopic interactions between players are nearly always asymmetric due to environmental effects, differing baseline characteristics, and other possible sources of heterogeneity. To model these phenomena, we introduce into evolutionary game theory two broad classes of asymmetric interactions: ecological and genotypic. Ecological asymmetry results from variation in the environments of the players, while genotypic asymmetry is a consequence of the players having differing baseline genotypes. We develop a theory of these forms of asymmetry for games in structured populations and use the classical social dilemmas, the Prisoner's Dilemma and the Snowdrift Game, for illustrations. Interestingly, asymmetric games reveal essential differences between models of genetic evolution based on reproduction and models of cultural evolution based on imitation that are not apparent in symmetric games. PMID:26308326

  11. Oscillating asymmetric dark matter

    SciTech Connect

    Tulin, Sean; Yu, Hai-Bo; Zurek, Kathryn M. E-mail: haiboyu@umich.edu

    2012-05-01

    We study the dynamics of dark matter (DM) particle-antiparticle oscillations within the context of asymmetric DM. Oscillations arise due to small DM number-violating Majorana-type mass terms, and can lead to recoupling of annihilation after freeze-out and washout of the DM density. Asymmetric DM oscillations 'interpolate' between symmetric and asymmetric DM freeze-out scenarios, and allow for a larger DM model-building parameter space. We derive the density matrix equations for DM oscillations and freeze-out from first principles using nonequilibrium field theory, and our results are qualitatively different than in previous studies. DM dynamics exhibits particle-vs-antiparticle 'flavor' effects, depending on the interaction type, analogous to neutrino oscillations in a medium. 'Flavor-sensitive' DM interactions include scattering or annihilation through a new vector boson, while 'flavor-blind' interactions include scattering or s-channel annihilation through a new scalar boson. In particular, we find that flavor-sensitive annihilation does not recouple when coherent oscillations begin, and that flavor-blind scattering does not lead to decoherence.

  12. Asymmetrical Capacitors for Propulsion

    NASA Technical Reports Server (NTRS)

    Canning, Francis X.; Melcher, Cory; Winet, Edwin

    2004-01-01

    Asymmetrical Capacitor Thrusters have been proposed as a source of propulsion. For over eighty years, it has been known that a thrust results when a high voltage is placed across an asymmetrical capacitor, when that voltage causes a leakage current to flow. However, there is surprisingly little experimental or theoretical data explaining this effect. This paper reports on the results of tests of several Asymmetrical Capacitor Thrusters (ACTs). The thrust they produce has been measured for various voltages, polarities, and ground configurations and their radiation in the VHF range has been recorded. These tests were performed at atmospheric pressure and at various reduced pressures. A simple model for the thrust was developed. The model assumed the thrust was due to electrostatic forces on the leakage current flowing across the capacitor. It was further assumed that this current involves charged ions which undergo multiple collisions with air. These collisions transfer momentum. All of the measured data was consistent with this model. Many configurations were tested, and the results suggest general design principles for ACTs to be used for a variety of purposes.

  13. Asymmetric Evolutionary Games

    PubMed Central

    McAvoy, Alex; Hauert, Christoph

    2015-01-01

    Evolutionary game theory is a powerful framework for studying evolution in populations of interacting individuals. A common assumption in evolutionary game theory is that interactions are symmetric, which means that the players are distinguished by only their strategies. In nature, however, the microscopic interactions between players are nearly always asymmetric due to environmental effects, differing baseline characteristics, and other possible sources of heterogeneity. To model these phenomena, we introduce into evolutionary game theory two broad classes of asymmetric interactions: ecological and genotypic. Ecological asymmetry results from variation in the environments of the players, while genotypic asymmetry is a consequence of the players having differing baseline genotypes. We develop a theory of these forms of asymmetry for games in structured populations and use the classical social dilemmas, the Prisoner’s Dilemma and the Snowdrift Game, for illustrations. Interestingly, asymmetric games reveal essential differences between models of genetic evolution based on reproduction and models of cultural evolution based on imitation that are not apparent in symmetric games. PMID:26308326

  14. Asymmetric Latent Carbocation Catalysis with Chiral Trityl Phosphate.

    PubMed

    Lv, Jian; Zhang, Qichao; Zhong, Xingren; Luo, Sanzhong

    2015-12-16

    Stable carbocations such as tritylium ions have been widely explored as organic Lewis acid catalysts and reagents in organic synthesis. However, achieving asymmetric carbocation catalysis remains elusive ever since they were first identified over one century ago. The challenges mainly come from their limited compatibility, scarcity of chiral carbocations, as well as the extremely low barrier to racemization of chiral carbenium ions. We reported here a latent concept for asymmetric carbocation catalysis. In this strategy, chiral trityl phosphate is employed as the carbocation precursor, which undergoes facile ionic dissociation upon mild external stimulation (e.g., acid, H-bonding, polar substrates) to form a catalytically active chiral ion pair for substrate activation and chiral induction. The latent strategy provides a solution for the long sought-after asymmetric carbocation catalysis as illustrated in three different enantioselective transformations. PMID:26594778

  15. Absolute calibration of optical flats

    SciTech Connect

    Sommargren, Gary E.

    2005-04-05

    The invention uses the phase shifting diffraction interferometer (PSDI) to provide a true point-by-point measurement of absolute flatness over the surface of optical flats. Beams exiting the fiber optics in a PSDI have perfect spherical wavefronts. The measurement beam is reflected from the optical flat and passed through an auxiliary optic to then be combined with the reference beam on a CCD. The combined beams include phase errors due to both the optic under test and the auxiliary optic. Standard phase extraction algorithms are used to calculate this combined phase error. The optical flat is then removed from the system and the measurement fiber is moved to recombine the two beams. The newly combined beams include only the phase errors due to the auxiliary optic. When the second phase measurement is subtracted from the first phase measurement, the absolute phase error of the optical flat is obtained.

  16. Absolute pitch and planum temporale.

    PubMed

    Keenan, J P; Thangaraj, V; Halpern, A R; Schlaug, G

    2001-12-01

    An increased leftward asymmetry of the planum temporale (PT) in absolute-pitch (AP) musicians has been previously reported, with speculation that early exposure to music influences the degree of PT asymmetry. To test this hypothesis and to determine whether a larger left PT or a smaller right PT actually accounts for the increased overall PT asymmetry in AP musicians, anatomical magnetic resonance images were taken from a right-handed group of 27 AP musicians, 27 nonmusicians, and 22 non-AP musicians. A significantly greater leftward PT asymmetry and a significantly smaller right absolute PT size for the AP musicians compared to the two control groups was found, while the left PT was only marginally larger in the AP group. The absolute size of the right PT and not the left PT was a better predictor of music group membership, possibly indicating "pruning" of the right PT rather than expansion of the left underlying the increased PT asymmetry in AP musicians. Although early exposure to music may be a prerequisite for acquiring AP, the increased PT asymmetry in AP musicians may be determined in utero, implicating possible genetic influences on PT asymmetry. This may explain why the increased PT asymmetry of AP musicians was not seen in the group of early beginning non-AP musicians. PMID:11707095

  17. Pd-Catalyzed Asymmetric ?-Hydride Elimination En Route to Chiral Allenes

    PubMed Central

    Crouch, Ian T.; Neff, Robynne K.; Frantz, Doug E.

    2013-01-01

    We wish to report our preliminary results on the discovery and development of a catalytic, asymmetric ?-hydride elimination from vinyl Pd(II)-complexes derived from enol triflates to access chiral allenes. To achieve this, we developed a class of chiral phosphite ligands that demonstrate high enantioselectivity, allow access of either allene enantiomer, and are readily synthesized. The methodology is demonstrated on over 20 substrates and application to the formal asymmetric total synthesis of the natural product, (+)-epibatidine, is also provided. PMID:23488914

  18. Asymmetric inclusion process

    NASA Astrophysics Data System (ADS)

    Reuveni, Shlomi; Eliazar, Iddo; Yechiali, Uri

    2011-10-01

    We introduce and explore the asymmetric inclusion process (ASIP), an exactly solvable bosonic counterpart of the fermionic asymmetric exclusion process (ASEP). In both processes, random events cause particles to propagate unidirectionally along a one-dimensional lattice of n sites. In the ASEP, particles are subject to exclusion interactions, whereas in the ASIP, particles are subject to inclusion interactions that coalesce them into inseparable clusters. We study the dynamics of the ASIP, derive evolution equations for the mean and probability generating function (PGF) of the sites’ occupancy vector, obtain explicit results for the above mean at steady state, and describe an iterative scheme for the computation of the PGF at steady state. We further obtain explicit results for the load distribution in steady state, with the load being the total number of particles present in all lattice sites. Finally, we address the problem of load optimization, and solve it under various criteria. The ASIP model establishes bridges between statistical physics and queueing theory as it represents a tandem array of queueing systems with (unlimited) batch service, and a tandem array of growth-collapse processes.

  19. Colon Cryptogenesis: Asymmetric Budding

    PubMed Central

    Tan, Chin Wee; Hirokawa, Yumiko; Gardiner, Bruce S.; Smith, David W.; Burgess, Antony W.

    2013-01-01

    The process of crypt formation and the roles of Wnt and cell-cell adhesion signaling in cryptogenesis are not well described; but are important to the understanding of both normal and cancer colon crypt biology. A quantitative 3D-microscopy and image analysis technique is used to study the frequency, morphology and molecular topography associated with crypt formation. Measurements along the colon reveal the details of crypt formation and some key underlying biochemical signals regulating normal colon biology. Our measurements revealed an asymmetrical crypt budding process, contrary to the previously reported symmetrical fission of crypts. 3D immunofluorescence analyses reveals heterogeneity in the subcellular distribution of E-cadherin and ?-catenin in distinct crypt populations. This heterogeneity was also found in asymmetrical budding crypts. Singular crypt formation (i.e. no multiple new crypts forming from one parent crypt) were observed in crypts isolated from the normal colon mucosa, suggestive of a singular constraint mechanism to prevent aberrant crypt production. The technique presented improves our understanding of cryptogenesis and suggests that excess colon crypt formation occurs when Wnt signaling is perturbed (e.g. by truncation of adenomatous polyposis coli, APC protein) in most colon cancers. PMID:24205248

  20. Hunting Asymmetric Stops

    E-print Network

    Michael L. Graesser; Jessie Shelton

    2013-10-06

    We point out that in the irreducible natural SUSY spectrum, stops have comparable branching fractions to chargino-bottom and neutralino-top in the vast bulk of parameter space, provided only that both decay modes are kinematically accessible. The total stop pair branching fractions into ttbar + MET can therefore be reduced to O(50%), while b bbar + X branching fractions are typically much smaller, O(10%), thus limiting the reach of traditional stop searches. We propose a new stop search targeting the asymmetric final state \\~t\\~t* --> t chi^0 b chi^pm, which can restore sensitivity to natural stops in the 7 and 8 TeV LHC runs. In addition we present a new variable, topness, which efficiently suppresses the dominant top backgrounds to semi-leptonic top partner searches. We demonstrate the utility of topness in both our asymmetric search channel and traditional \\~t\\~t* --> ttbar + MET searches and show that it matches or out-performs existing variables.

  1. Optimal Asymmetric Quantum Cloning

    E-print Network

    Alastair Kay; Ravishankar Ramanathan; Dagomir Kaszlikowski

    2012-08-28

    While the no-cloning theorem, which forbids the perfect copying of quantum states, is well-known as one of the defining features of quantum mechanics, the question of how well the theory allows a state to be cloned is yet to be completely solved. In this paper, rigorous solutions to the problem of M to N asymmetric cloning of qudits are obtained in a number of interesting cases. The central result is the solution to the 1 to N universal asymmetric qudit cloning problem for which the exact trade-off in the fidelities of the clones for every N and d is derived. Analogous results are proven for qubits when M=N-1. We also consider state-dependent 1 to N qubit cloning, providing a general parametrization in terms of a Heisenberg star Hamiltonian. In all instances, we determine the feasibility of implementing the cloning economically, i.e., without an ancilla, and determine the dimension of the ancilla when an economic implementation is not possible.

  2. Asymmetric photoredox transition-metal catalysis activated by visible light

    NASA Astrophysics Data System (ADS)

    Huo, Haohua; Shen, Xiaodong; Wang, Chuanyong; Zhang, Lilu; Röse, Philipp; Chen, Liang-An; Harms, Klaus; Marsch, Michael; Hilt, Gerhard; Meggers, Eric

    2014-11-01

    Asymmetric catalysis is seen as one of the most economical strategies to satisfy the growing demand for enantiomerically pure small molecules in the fine chemical and pharmaceutical industries. And visible light has been recognized as an environmentally friendly and sustainable form of energy for triggering chemical transformations and catalytic chemical processes. For these reasons, visible-light-driven catalytic asymmetric chemistry is a subject of enormous current interest. Photoredox catalysis provides the opportunity to generate highly reactive radical ion intermediates with often unusual or unconventional reactivities under surprisingly mild reaction conditions. In such systems, photoactivated sensitizers initiate a single electron transfer from (or to) a closed-shell organic molecule to produce radical cations or radical anions whose reactivities are then exploited for interesting or unusual chemical transformations. However, the high reactivity of photoexcited substrates, intermediate radical ions or radicals, and the low activation barriers for follow-up reactions provide significant hurdles for the development of efficient catalytic photochemical processes that work under stereochemical control and provide chiral molecules in an asymmetric fashion. Here we report a highly efficient asymmetric catalyst that uses visible light for the necessary molecular activation, thereby combining asymmetric catalysis and photocatalysis. We show that a chiral iridium complex can serve as a sensitizer for photoredox catalysis and at the same time provide very effective asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles. This new asymmetric photoredox catalyst, in which the metal centre simultaneously serves as the exclusive source of chirality, the catalytically active Lewis acid centre, and the photoredox centre, offers new opportunities for the `green' synthesis of non-racemic chiral molecules.

  3. Absolute versus convective instability of spiral waves

    PubMed

    Sandstede; Scheel

    2000-12-01

    Absolute and convective instabilities of spirals are investigated using the continuous and the so-called absolute spectrum. It is shown that the nature of transport, induced by an absolute instability, is determined by spectral data of the asymptotic wave trains. The results are applied to core and far-field breakup of spiral waves in excitable and oscillatory media. PMID:11138042

  4. Familial aggregation of absolute pitch.

    PubMed

    Baharloo, S; Service, S K; Risch, N; Gitschier, J; Freimer, N B

    2000-09-01

    Absolute pitch (AP) is a behavioral trait that is defined as the ability to identify the pitch of tones in the absence of a reference pitch. AP is an ideal phenotype for investigation of gene and environment interactions in the development of complex human behaviors. Individuals who score exceptionally well on formalized auditory tests of pitch perception are designated as "AP-1." As described in this report, auditory testing of siblings of AP-1 probands and of a control sample indicates that AP-1 aggregates in families. The implications of this finding for the mapping of loci for AP-1 predisposition are discussed. PMID:10924408

  5. Absolute calibration of optical tweezers

    SciTech Connect

    Viana, N.B.; Mazolli, A.; Maia Neto, P.A.; Nussenzveig, H.M.; Rocha, M.S.; Mesquita, O.N.

    2006-03-27

    As a step toward absolute calibration of optical tweezers, a first-principles theory of trapping forces with no adjustable parameters, corrected for spherical aberration, is experimentally tested. Employing two very different setups, we find generally very good agreement for the transverse trap stiffness as a function of microsphere radius for a broad range of radii, including the values employed in practice, and at different sample chamber depths. The domain of validity of the WKB ('geometrical optics') approximation to the theory is verified. Theoretical predictions for the trapping threshold, peak position, depth variation, multiple equilibria, and 'jump' effects are also confirmed.

  6. Absolute calibration of optical tweezers

    NASA Astrophysics Data System (ADS)

    Viana, N. B.; Mazolli, A.; Maia Neto, P. A.; Nussenzveig, H. M.; Rocha, M. S.; Mesquita, O. N.

    2006-03-01

    As a step toward absolute calibration of optical tweezers, a first-principles theory of trapping forces with no adjustable parameters, corrected for spherical aberration, is experimentally tested. Employing two very different setups, we find generally very good agreement for the transverse trap stiffness as a function of microsphere radius for a broad range of radii, including the values employed in practice, and at different sample chamber depths. The domain of validity of the WKB ("geometrical optics") approximation to the theory is verified. Theoretical predictions for the trapping threshold, peak position, depth variation, multiple equilibria, and "jump" effects are also confirmed.

  7. Preparation of asymmetric porous materials

    DOEpatents

    Coker, Eric N. (Albuquerque, NM)

    2012-08-07

    A method for preparing an asymmetric porous material by depositing a porous material film on a flexible substrate, and applying an anisotropic stress to the porous media on the flexible substrate, where the anisotropic stress results from a stress such as an applied mechanical force, a thermal gradient, and an applied voltage, to form an asymmetric porous material.

  8. Models for asymmetric hybrid brane

    NASA Astrophysics Data System (ADS)

    Bazeia, D.; Marques, M. A.; Menezes, R.

    2015-10-01

    We deal with relativistic models described by a single real scalar field, searching for topological structures that behave asymmetrically, connecting minima with a distinct profile. We use such features to build a new braneworld scenario, in which the source scalar field contributes to generate asymmetric hybrid brane.

  9. Studies of stereocontrolled allylation reactions for the total synthesis of phorboxazole A

    PubMed Central

    Williams, David R.; Kiryanov, Andre A.; Emde, Ulrich; Clark, Michael P.; Berliner, Martin A.; Reeves, Jonathan T.

    2004-01-01

    A highly convergent total synthesis of the potent anticancer agent (+)-phorboxazole A (1) is accomplished. Four components (3–6) are assembled with considerations for control of absolute and relative stereochemistry. Iterative asymmetric allylation methodology addresses key stereochemical features in the preparation of the 2,6-cis- and 2,6-trans-tetrahydropyranyl rings of the C3–C19 component (3). The stereocontrolled asymmetric allylation process is also used for development of the C28–C41 fragment (4). Novel Barbier coupling reactions of ?-iodomethyl oxazoles and related thiazoles are described with samarium iodide. The convergent assembly of components 4 and 5 features formation of the fully substituted C22–C26 pyran by intramolecular capture of an allyl cation intermediate with high facial selectivity, and further efforts lead to E-C19/C20 olefination. The synthesis culminates with use of a modified Julia olefination for attachment of the C42–C46 segment and subsequent late-stage macrocyclization by installation of the (Z)-C2/C3 ?,?-unsaturated lactone. PMID:15277662

  10. Asymmetric twin Dark Matter

    NASA Astrophysics Data System (ADS)

    Farina, Marco

    2015-11-01

    We study a natural implementation of Asymmetric Dark Matter in Twin Higgs models. The mirroring of the Standard Model strong sector suggests that a twin baryon with mass around 5 GeV is a natural Dark Matter candidate once a twin baryon number asymmetry comparable to the SM asymmetry is generated. We explore twin baryon Dark Matter in two different scenarios, one with minimal content in the twin sector and one with a complete copy of the SM, including a light twin photon. The essential requirements for successful thermal history are presented, and in doing so we address some of the cosmological issues common to many Twin Higgs models. The required interactions we introduce predict signatures at direct detection experiments and at the LHC.

  11. Minimal asymmetric dark matter

    NASA Astrophysics Data System (ADS)

    Boucenna, Sofiane M.; Krauss, Martin B.; Nardi, Enrico

    2015-09-01

    In the early Universe, any particle carrying a conserved quantum number and in chemical equilibrium with the thermal bath will unavoidably inherit a particle-antiparticle asymmetry. A new particle of this type, if stable, would represent a candidate for asymmetric dark matter (DM) with an asymmetry directly related to the baryon asymmetry. We study this possibility for a minimal DM sector constituted by just one (generic) SU (2)L multiplet ? carrying hypercharge, assuming that at temperatures above the electroweak phase transition an effective operator enforces chemical equilibrium between ? and the Higgs boson. We argue that limits from DM direct detection searches severely constrain this scenario, leaving as the only possibilities scalar or fermion multiplets with hypercharge y = 1, preferentially quintuplets or larger SU (2) representations, and with a mass in the few TeV range.

  12. Asymmetric Higgsino dark matter.

    PubMed

    Blum, Kfir; Efrati, Aielet; Grossman, Yuval; Nir, Yosef; Riotto, Antonio

    2012-08-01

    In the supersymmetric framework, prior to the electroweak phase transition, the existence of a baryon asymmetry implies the existence of a Higgsino asymmetry. We investigate whether the Higgsino could be a viable asymmetric dark matter candidate. We find that this is indeed possible. Thus, supersymmetry can provide the observed dark matter abundance and, furthermore, relate it with the baryon asymmetry, in which case the puzzle of why the baryonic and dark matter mass densities are similar would be explained. To accomplish this task, two conditions are required. First, the gauginos, squarks, and sleptons must all be very heavy, such that the only electroweak-scale superpartners are the Higgsinos. With this spectrum, supersymmetry does not solve the fine-tuning problem. Second, the temperature of the electroweak phase transition must be low, in the (1-10) GeV range. This condition requires an extension of the minimal supersymmetric standard model. PMID:23006163

  13. Minimal Asymmetric Dark Matter

    E-print Network

    Boucenna, Sofiane M; Nardi, Enrico

    2015-01-01

    In the early Universe, any particle carrying a conserved quantum number and in chemical equilibrium with the thermal bath will unavoidably inherit a particle-antiparticle asymmetry. A new particle of this type, if stable, would represent a candidate for asymmetric dark matter (DM) with an asymmetry directly related to the baryon asymmetry. We study this possibility for a minimal DM sector constituted by just one (generic) $SU(2)_L$ multiplet $\\chi$ carrying hypercharge, assuming that at temperatures above the electroweak phase transition an effective operator enforces chemical equilibrium between $\\chi$ and the Higgs boson. We argue that limits from DM direct detection searches severely constrain this scenario, ruling out the possibility of scalar multiplets, and leaving as the only possibilities fermion DM with hypercharge $y = 1/2$ and $y = 1$ with a mass in the few TeV range.

  14. Catalytic asymmetric umpolung reactions of imines

    NASA Astrophysics Data System (ADS)

    Wu, Yongwei; Hu, Lin; Li, Zhe; Deng, Li

    2015-07-01

    The carbon-nitrogen double bonds in imines are fundamentally important functional groups in organic chemistry. This is largely due to the fact that imines act as electrophiles towards carbon nucleophiles in reactions that form carbon-carbon bonds, thereby serving as one of the most widely used precursors for the formation of amines in both synthetic and biosynthetic settings. If the carbon atom of the imine could be rendered electron-rich, the imine could react as a nucleophile instead of as an electrophile. Such a reversal in the electronic characteristics of the imine functionality would facilitate the development of new chemical transformations that convert imines into amines via carbon-carbon bond-forming reactions with carbon electrophiles, thereby creating new opportunities for the efficient synthesis of amines. The development of asymmetric umpolung reactions of imines (in which the imines act as nucleophiles) remains uncharted territory, in spite of the far-reaching impact such reactions would have in organic synthesis. Here we report the discovery and development of new chiral phase-transfer catalysts that promote the highly efficient asymmetric umpolung reactions of imines with the carbon electrophile enals. These catalysts mediate the deprotonation of imines and direct the 2-azaallyl anions thus formed to react with enals in a highly chemoselective, regioselective, diastereoselective and enantioselective fashion. The reaction tolerates a broad range of imines and enals, and can be carried out in high yield with as little as 0.01 mole per cent catalyst with a moisture- and air-tolerant operational protocol. These umpolung reactions provide a conceptually new and practical approach to chiral amino compounds.

  15. Stereodivergent Synthesis of Chiral Fullerenes by [3 + 2] Cycloadditions to C60

    PubMed Central

    2013-01-01

    A wide range of new dipoles and catalysts have been used in 1,3-dipolar cycloadditions of N-metalated azomethine ylides onto C60 yielding a full stereodivergent synthesis of pyrrolidino[60]fullerenes with complete diastereoselectivities and very high enantioselectivities. The use of less-explored chiral ?-iminoamides as starting 1,3-dipoles leads to an interesting double asymmetric induction resulting in a matching/mismatching effect depending upon the absolute configuration of the stereocenter in the starting ?-iminoamide. An enantioselective process was also found in the retrocycloaddition reaction as revealed by mass spectrometry analysis on quasi-enantiomeric pyrrolidino[60]fullerenes. Theoretical DFT calculations are in very good agreement with the experimental data. On the basis of this agreement, a plausible reaction mechanism is proposed. PMID:24359021

  16. Nonracemic synthesis of GK-GKRP disruptor AMG-3969.

    PubMed

    Bourbeau, Matthew P; Ashton, Kate S; Yan, Jie; St Jean, David J

    2014-04-18

    A nonracemic synthesis of the glucokinase-glucokinase regulatory protein disruptor AMG-3969 (5) is reported. Key features of the synthetic approach are an asymmetric synthesis of the 2-alkynyl piperazine core via a base-promoted isomerization and a revised approach to the synthesis of the aminopyridinesulfonamide with an improved safety profile. PMID:24678849

  17. "Absolute" sterility and "absolute" freedom from particle contamination.

    PubMed

    Knapp, J Z

    1998-01-01

    Until the recent past, sterility of an injectable product was only discussed in absolute terms. Any description of sterility other than as an absolute could simply not be envisioned. While dealing in absolute yes/no statements is philosophically satisfying, these yes/no statements can't accommodate all real world scientific problems. Among these problems is the sterility problems faced in the mass production of injectable compounds. Many descriptions of procedures employed to achieve sterility in parenteral production batches were reported in the literature. The theoretical framework that could unite the widespread observations and practices into practical methodology was missing until recently. Production line control of the sterility of injectable products was essentially based on gut evaluations. The present achievement of rational, production line control of product sterility is based on the recognition that product sterility could not be simply regarded as a sharply edged yes/no affair. The present rational control is based on the fact that the sterility of a product is determined by the degree of contamination in the product prior to sterilization and to the parameters of the sterilization process. The end result of the sterilization process is now described as a probabalistic reduction of the initial contamination. The essential laboratory measurements on which this conclusion was based is due to Pflug (1-3). He assembled a theoretical framework, based on experimental data, that characterizes the sterility achieved in an injectable product with a single number. The end result of the sterilization process is now described as a probabalistic reduction of the initial contamination. As in many disciplines, the ability to achieve an objective evaluation of this important attribute provided the basis for scientific analysis, improved control and thus improved production and reduced cost. An equivalent framework is essential for the communication and standardization of the results of a visual inspection for contaminating particles. The control of particle contamination in injectable products is a two-fold problem for the pharmaceutical industry. The two parts of the problem are 1) achieving contamination free product and 2) achieving this contamination free quality at an economic cost acceptable to the user. Today, there is no commonly accepted framework for the definition or analysis of the results of a manual inspection for "visible" particles. Any progress toward global harmonization of the results of a visual particle inspection must commence with the development of a common scientific language with which inspection security and economic effectiveness of an inspection can be discussed and rationally evaluated. The tools with which to define and control the results of this inspection have been developed in biophysics, illumination engineering, optics, pharmaceutical manufacturing and statistics. With them, statistically replicable measures have been developed. The statistically replicable measures are then used to evaluate the results of semi- and fully automated particle inspection systems in terms of human inspection performance. The numerical evaluation of both the freedom from contamination achieved with an inspection for particle contamination and the economic effectiveness of the inspection are compared to Pflug's sterility index. In the case of particle contamination, the final product quality depends on product quality prior to inspection and to the parameters of the inspection process. PMID:9752713

  18. Catalytic enantioselective synthesis of naturally occurring butenolides via hetero-allylic alkylation and ring closing metathesis.

    PubMed

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; van Zijl, Anthoni W; Fletcher, Stephen P; Minnaard, Adriaan J; Feringa, Ben L

    2011-03-01

    An efficient catalytic asymmetric synthesis of chiral ?-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey lactone, (-)-cognac lactone, (-)-nephrosteranic acid, and (-)-roccellaric acid. PMID:21268603

  19. Synthesis and Suzuki-Miyaura Cross-Coupling of Enantioenriched Secondary Potassium ?-Trifluoroboratoamides: Catalytic, Asymmetric Conjugate Addition of Bisboronic Acid and Tetrakis(dimethylamino)diboron to ?,?-Unsaturated Carbonyl Compounds

    PubMed Central

    Wisniewski, Steven R.; Hosseini-Sarvari, Mona

    2014-01-01

    Enantioenriched potassium ?-trifluoroboratoamides have been synthesized via an asymmetric, copper-catalyzed 1,4-addition of tetrahydroxydiboron (BBA) and tetrakis(dimethylamino)diboron to ?,?-unsaturated amides. These dibora reagents provide access to the desired organotrifluoroborates using effective and atom economical sources of boron. The copper-catalyzed ?-boration is extended to ?,?-unsaturated ketones and esters. Desired potassium organotrifluoroborates are synthesized with yields up to 92% and enantiomeric ratios up to 98:2. The enantioenriched potassium ?-trifluoroboratoamides are successfully cross-coupled with an array of aryl and heteroaryl chlorides in high yield with complete stereochemical fidelity as the transmetalation proceeds through an SE2 mechanism via an open transition state. PMID:24741373

  20. Substrate-Controlled Asymmetric Total Syntheses of Microcladallenes?A, B, and C Based on the Proposed Structures.

    PubMed

    Sohn, Te-Ik; Kim, Deukjoon; Paton, Robert S

    2015-11-01

    Substrate-controlled asymmetric total syntheses of (+)-microcladallenes?A, B, and C have been accomplished based on the proposed structures. The syntheses of microcladallenes?A and B confirmed the structures and absolute configurations of both natural products. However, the synthesis of microcladallene?C, which includes seven stereogenic centers and an (R)-bromoallene in its compact C15 framework, brought the realization that its proposed structure must be revised. The introduction of C12-bromine into these natural products with retention of configuration relied on TiBr4 -mediated nucleophile-assisting leaving group brominations, the stereochemical outcome of which could be attributed, at least in part, to an oxonium or halonium ion formation-fragmentation sequence through intricate neighboring group participation. In addition, the pivotal ?-oriented vicinal cis-dichloride function in microcladallene?C was elaborated through a novel tandem Cl2 -induced electrophilic cyclization/imidate chlorination process. The positive rotations of these natural products with an (R)-bromoallene constitute exceptions to Lowe's rule for reasons yet to be determined. PMID:26376617

  1. Extremal asymmetric universal cloning machines

    E-print Network

    Mingming Jiang; Sixia Yu

    2012-02-08

    The trade-offs among various output fidelities of asymmetric universal cloning machines are investigated. First we find out all the attainable optimal output fidelities for the 1 to 3 asymmetric universal cloning machine and it turns out that there are two kinds of extremal asymmetric cloning machines which have to cooperate in order to achieve some of the optimal output fidelities. Second we construct a family of extremal cloning machines that includes the universal symmetric cloning machine as well as an asymmetric 1 to $1+N$ cloning machine for qudits with two different output fidelities such that the optimal trade-off between the measurement disturbance and state estimation is attained in the limit of infinite $N$.

  2. Entrapment of a chiral cobalt complex within silver: a novel heterogeneous catalyst for asymmetric carboxylation of benzyl bromides with CO2.

    PubMed

    Yang, Heng-Pan; Yue, Ying-Na; Sun, Qi-Long; Feng, Qiu; Wang, Huan; Lu, Jia-Xing

    2015-08-01

    A novel way to accommodate heterogeneous catalysis, CO2 fixation and asymmetric synthesis on one catalyst is reported. The [Co]@Ag composite was prepared for the first time and used for asymmetric carboxylation of benzyl bromides with CO2. All the procedures were performed under mild conditions. Moreover, the [Co]@Ag composite has terrific stability and reusability. PMID:26134479

  3. Asymmetric hydroformylation of Z-enamides and enol esters with rhodium-bisdiazaphos catalysts.

    PubMed

    Abrams, M Leigh; Foarta, Floriana; Landis, Clark R

    2014-10-15

    Asymmetric hydroformylation (AHF) of Z-enamides and Z-enol esters provides chiral, alpha-functionalized aldehydes with high selectivity and atom economy. Rh-bisdiazaphospholane catalysts enable hydroformylation of these challenging disubstituted substrates under mild reaction conditions and low catalyst loadings. The synthesis of a protected analog of l-DOPA demonstrates the utility of AHF for enantioselective, atom-efficient synthesis of peptide precursors. PMID:25241657

  4. Absolute negative mobility of interacting Brownian particles

    NASA Astrophysics Data System (ADS)

    Ou, Ya-li; Hu, Cai-tian; Wu, Jian-chun; Ai, Bao-quan

    2015-12-01

    Transport of interacting Brownian particles in a periodic potential is investigated in the presence of an ac force and a dc force. From Brownian dynamic simulations, we find that both the interaction between particles and the thermal fluctuations play key roles in the absolute negative mobility (the particle noisily moves backwards against a small constant bias). When no the interaction acts, there is only one region where the absolute negative mobility occurs. In the presence of the interaction, the absolute negative mobility may appear in multiple regions. The weak interaction can be helpful for the absolute negative mobility, while the strong interaction has a destructive impact on it.

  5. Asymmetric 1,4-bis(ethynyl)bicyclo[2.2.2]octane rotators via monocarbinol functionalization. Ready access to polyrotors

    PubMed Central

    2015-01-01

    Summary Asymmetric rotators with a 1,4-bis(ethynyl)bicyclo[2.2.2]octane (BCO) core are needed for engineering crystalline arrays of functional molecular rotors. Their synthesis uses carbinol, 2-methyl-3-butyn-2-ol, as a protecting group because of its polar character and its ability to sustain orthogonal functionalization with the further advantage of being readily removed. The synthesis in good yields of unprecedented asymmetric rotors and polyrotors demonstrates the efficiency of this strategy. PMID:26664606

  6. Tandem Reactions for Streamlining Synthesis

    PubMed Central

    HUSSAIN, MAHMUD M.; WALSH, PATRICK J.

    2009-01-01

    CONSPECTUS In 1980 Sharpless and Katsuki introduced the asymmetric epoxidation of prochiral allylic alcohols (the Sharpless-Katsuki Asymmetric Epoxidation), which enabled the rapid synthesis of highly enantioenriched epoxy alcohols. This reaction was a milestone in the development of asymmetric catalysis because it was the first highly enantioselective oxidation reaction. Furthermore, it provided access to enantioenriched allylic alcohols that are now standard starting materials in natural product synthesis. In 1981 Sharpless and coworkers made another seminal contribution by describing the kinetic resolution (KR) of racemic allylic alcohols. This work demonstrated that small-molecule catalysts could compete with enzymatic catalysts in KRs. For these pioneering works, Sharpless was awarded the 2001 Nobel Prize with Knowles and Noyori. Despite these achievements, the Sharpless KR is not an efficient method to prepare epoxy alcohols with high enantiomeric excess (ee). First, the racemic allylic alcohol must be prepared and purified. KR of the racemic allylic alcohol must be stopped at low conversion, because the ee of the product epoxy alcohol decreases as the KR progresses. Thus, better methods to prepare epoxy alcohols containing stereogenic carbinol carbons are needed. This Account summarizes our efforts to develop one-pot methods for the synthesis of various epoxy alcohols and allylic epoxy alcohols with high enantio-, diastereo-, and chemoselectivity. Our laboratory developed titanium-based catalysts for use in the synthesis of epoxy alcohols with tertiary carbinols. The catalysts are involved in the first step, which is an asymmetric alkyl or allyl addition to enones. The resulting intermediates are then subjected to a titanium-directed diastereoselective epoxidation to provide tertiary epoxy alcohols. Similarly, the synthesis of acyclic epoxy alcohols begins with asymmetric additions to enals and subsequent epoxidation. The methods described here enable the synthesis of skeletally diverse epoxy alcohols. PMID:18710197

  7. Divertissement 4: Absolute Temperature From Thermodynamics

    E-print Network

    Ronis, David M.

    Divertissement 4: Absolute Temperature From Thermodynamics (North Holland, 1976) Ryogo Kubo by a thermodynamic method so that it does not depend on the choice of thermometric substance, the zero of the scale being defined as the lowest temperature which is possible thermodynamically. Absolute temperature, which

  8. Absolute optical metrology : nanometers to kilometers

    NASA Technical Reports Server (NTRS)

    Dubovitsky, Serge; Lay, O. P.; Peters, R. D.; Liebe, C. C.

    2005-01-01

    We provide and overview of the developments in the field of high-accuracy absolute optical metrology with emphasis on space-based applications. Specific work on the Modulation Sideband Technology for Absolute Ranging (MSTAR) sensor is described along with novel applications of the sensor.

  9. Absolute instabilities of standing pulses Bjorn Sandstede

    E-print Network

    Scheel, Arnd

    Absolute instabilities of standing pulses Bj¨orn Sandstede Department of Mathematics The Ohio State-diffusion systems that are caused by an absolute instability of the homogeneous background state. Specifically, we renders the instability convective in nature [18, 19]: Even though perturbations grow in overall amplitude

  10. Inequalities, Absolute Value, and Logical Connectives.

    ERIC Educational Resources Information Center

    Parish, Charles R.

    1992-01-01

    Presents an approach to the concept of absolute value that alleviates students' problems with the traditional definition and the use of logical connectives in solving related problems. Uses a model that maps numbers from a horizontal number line to a vertical ray originating from the origin. Provides examples solving absolute value equations and…

  11. Introducing the Mean Absolute Deviation "Effect" Size

    ERIC Educational Resources Information Center

    Gorard, Stephen

    2015-01-01

    This paper revisits the use of effect sizes in the analysis of experimental and similar results, and reminds readers of the relative advantages of the mean absolute deviation as a measure of variation, as opposed to the more complex standard deviation. The mean absolute deviation is easier to use and understand, and more tolerant of extreme…

  12. Absolute Income, Relative Income, and Happiness

    ERIC Educational Resources Information Center

    Ball, Richard; Chernova, Kateryna

    2008-01-01

    This paper uses data from the World Values Survey to investigate how an individual's self-reported happiness is related to (i) the level of her income in absolute terms, and (ii) the level of her income relative to other people in her country. The main findings are that (i) both absolute and relative income are positively and significantly…

  13. Symmetric and asymmetric charge transport in interacting asymmetric quantum impurities

    NASA Astrophysics Data System (ADS)

    Roy, Dibyendu

    2010-02-01

    We study steady-state charge transfer across an interacting resonance-level model connected asymmetrically to two leads. For a linear energy dispersion relation of the leads, we calculate current-voltage characteristics of the model exactly employing the scattering Bethe ansatz of Mehta-Andrei and find symmetric transport showing the absence of diode effect. Next we study a lattice version of this model with a nonlinear dispersion for the leads using the Lippmann-Schwinger scattering theory. We find that the inclusion of nonlinearity in the leads’ dispersion causes rectification for asymmetric junctions but does not rectify for asymmetric interactions and perfect junctions. The model in the latter case can be mapped into a model of a single noninteracting electron in higher dimensions.

  14. Quantum nonequilibrium equalities with absolute irreversibility

    NASA Astrophysics Data System (ADS)

    Funo, Ken; Murashita, Yûto; Ueda, Masahito

    2015-07-01

    We derive quantum nonequilibrium equalities in absolutely irreversible processes. Here by absolute irreversibility we mean that in the backward process the density matrix does not return to the subspace spanned by those eigenvectors that have nonzero weight in the initial density matrix. Since the initial state of a memory and the postmeasurement state of the system are usually restricted to a subspace, absolute irreversibility occurs during the measurement and feedback processes. An additional entropy produced in absolutely irreversible processes needs to be taken into account to derive nonequilibrium equalities. We discuss a model of a feedback control on a qubit system to illustrate the obtained equalities. By introducing N heat baths each composed of a qubit and letting them interact with the system, we show how the entropy reduction via feedback control can be converted into work. An explicit form of extractable work in the presence of absolute irreversibility is given.

  15. Synthesis, characterization and X-ray crystal structures of Vanadium(IV), Cobalt(III), Copper(II) and Zinc(II) complexes derived from an asymmetric bidentate Schiff-base ligand at ambient temperature

    NASA Astrophysics Data System (ADS)

    Khorshidifard, Mahsa; Amiri Rudbari, Hadi; Kazemi-Delikani, Zahra; Mirkhani, Valiollah; Azadbakht, Reza

    2015-02-01

    An asymmetric bidentate Schiff-base ligand (HL: 2-((allylimino)methyl)phenol) was prepared from reaction of salicylaldehyde and Allylamine. Vanadium(IV), Cobalt(III), Copper(II) and Zinc(II) complexes, VOL2, CoL3, CuL2 and ZnL2 were synthesized from the reaction of VO(acac)2, CoCl2·6H2O, CuCl2·2H2O and Zn(NO3)2·6H2O with the bidentate Schiff base ligand (HL: 2-allyliminomethyl-phenol) in methanol at ambient temperature. The ligand and its metal complexes were characterized by elemental analysis (CHN), FT-IR spectroscopy. In addition, 1H and 13C NMR techniques were employed for characterization of the ligand (HL) and diamagnetic complex ZnL2. The molecular structures of all complexes were determined by single crystal X-ray diffraction technique. In the ZnL2 and CuL2 complexes, the metal ion is coordinated by two nitrogen and two oxygen atoms from two Schiff base ligands in an approximately square planar trans-[MN2O2] coordination geometry. In the Vanadium(IV) complex, VOL2, the vanadium center in this structure has a distorted tetragonal pyramidal N2O3 coordination sphere and for Cobalt(III) complex, CoL3, the CoIII ion is six coordinated by three bidentate Schiff base ligands in a distorted octahedral environment.

  16. Asymmetric counterpropagating fronts without flow.

    PubMed

    Andrade-Silva, I; Clerc, M G; Odent, V

    2015-06-01

    Out-of-equilibrium systems exhibit domain walls between different states. These walls, depending on the type of connected states, can display rich spatiotemporal dynamics. In this Rapid Communication, we investigate the asymmetrical counterpropagation of fronts in an in-plane-switching cell filled with a nematic liquid crystal. Experimentally, we characterize the different front shapes and propagation speeds. These fronts present dissimilar elastic deformations that are responsible for their asymmetric speeds. Theoretically, using a phenomenological model, we describe the observed dynamics with fair agreement. PMID:26172647

  17. Asymmetric Organocatalysis at the Service of Medicinal Chemistry

    PubMed Central

    2014-01-01

    The application of the most representative and up-to-date examples of homogeneous asymmetric organocatalysis to the synthesis of molecules of interest in medicinal chemistry is reported. The use of different types of organocatalysts operative via noncovalent and covalent interactions is critically reviewed and the possibility of running some of these reactions on large or industrial scale is described. A comparison between the organo- and metal-catalysed methodologies is offered in several cases, thus highlighting the merits and drawbacks of these two complementary approaches to the obtainment of very popular on market drugs or of related key scaffolds. PMID:24971178

  18. Disulfonimide-Catalyzed Asymmetric Reduction of N-Alkyl Imines.

    PubMed

    Wakchaure, Vijay N; Kaib, Philip S J; Leutzsch, Markus; List, Benjamin

    2015-09-28

    A chiral disulfonimide (DSI)-catalyzed asymmetric reduction of N-alkyl imines with Hantzsch esters as a hydrogen source in the presence of Boc2 O has been developed. The reaction delivers Boc-protected N-alkyl amines with excellent yields and enantioselectivity. The method tolerates a large variety of alkyl amines, thus illustrating potential for a general reductive cross-coupling of ketones with diverse amines, and it was applied in the synthesis of the pharmaceuticals (S)-Rivastigmine, NPS R-568 Hydrochloride, and (R)-Fendiline. PMID:26382289

  19. Absolute vs. intensity-based emission caps

    E-print Network

    Ellerman, A. Denny.

    Cap-and-trade systems limit emissions to some pre-specified absolute quantity. Intensity-based limits, that restrict emissions to some pre-specified rate relative to input or output, are much more widely used in environmental ...

  20. Absolute magnitudes of trans-neptunian objects

    NASA Astrophysics Data System (ADS)

    Duffard, R.; Alvarez-candal, A.; Pinilla-Alonso, N.; Ortiz, J. L.; Morales, N.; Santos-Sanz, P.; Thirouin, A.

    2015-10-01

    Accurate measurements of diameters of trans- Neptunian objects are extremely complicated to obtain. Radiomatric techniques applied to thermal measurements can provide good results, but precise absolute magnitudes are needed to constrain diameters and albedos. Our objective is to measure accurate absolute magnitudes for a sample of trans- Neptunian objects, many of which have been observed, and modelled, by the "TNOs are cool" team, one of Herschel Space Observatory key projects grantes with ~ 400 hours of observing time. We observed 56 objects in filters V and R, if possible. These data, along with data available in the literature, was used to obtain phase curves and to measure absolute magnitudes by assuming a linear trend of the phase curves and considering magnitude variability due to rotational light-curve. In total we obtained 234 new magnitudes for the 56 objects, 6 of them with no reported previous measurements. Including the data from the literature we report a total of 109 absolute magnitudes.

  1. New absolute magnitude calibrations for detached binaries

    E-print Network

    S. Bilir; T. Ak; E. Soydugan; F. Soydugan; E. Yaz; N. Filiz Ak; Z. Eker; O. Demircan; M. Helvaci

    2008-06-07

    Lutz-Kelker bias corrected absolute magnitude calibrations for the detached binary systems with main-sequence components are presented. The absolute magnitudes of the calibrator stars were derived at intrinsic colours of Johnson-Cousins and 2MASS (Two Micron All Sky Survey) photometric systems. As for the calibrator stars, 44 detached binaries were selected from the Hipparcos catalogue, which have relative observed parallax errors smaller than 15% ($\\sigma_{\\pi}/\\pi\\leq0.15$). The calibration equations which provide the corrected absolute magnitude for optical and near-infrared pass bands are valid for wide ranges of colours and absolute magnitudes: $-0.18magnitude calibrations of this study can be used as a convenient statistical tool to estimate the true distances of detached binaries out of Hipparcos' distance limit.

  2. Magnifying absolute instruments for optically homogeneous regions

    SciTech Connect

    Tyc, Tomas

    2011-09-15

    We propose a class of magnifying absolute optical instruments with a positive isotropic refractive index. They create magnified stigmatic images, either virtual or real, of optically homogeneous three-dimensional spatial regions within geometrical optics.

  3. RESEARCH ARTICLE Asymmetric Evolutionary Games

    E-print Network

    Hauert, Christoph

    RESEARCH ARTICLE Asymmetric Evolutionary Games Alex McAvoy*, Christoph Hauert Department Evolutionary game theory is a powerful framework for studying evolution in populations of interacting individuals. A common assumption in evolutionary game theory is that interac- tions are symmetric, which means

  4. Absolutely uniform illumination of laser fusion pellets

    NASA Astrophysics Data System (ADS)

    Schmitt, A. J.

    1984-02-01

    Absolutely uniform illumination of spherical laser fusion pellets is possible when the energy deposition from a single laser beam is given by a simple cos 3 theta distribution. Conditions can be derived for which the laser beam targeting angles allow this absolute illumination uniformity. Configurations based upon the cube and higher order Platonic solids satisfy the constraints, as well as an infinite class of other less symmetric configurations.

  5. Absolute and relative quantification of RNA modifications via biosynthetic isotopomers

    PubMed Central

    Kellner, Stefanie; Ochel, Antonia; Thüring, Kathrin; Spenkuch, Felix; Neumann, Jennifer; Sharma, Sunny; Entian, Karl-Dieter; Schneider, Dirk; Helm, Mark

    2014-01-01

    In the resurging field of RNA modifications, quantification is a bottleneck blocking many exciting avenues. With currently over 150 known nucleoside alterations, detection and quantification methods must encompass multiple modifications for a comprehensive profile. LC–MS/MS approaches offer a perspective for comprehensive parallel quantification of all the various modifications found in total RNA of a given organism. By feeding 13C-glucose as sole carbon source, we have generated a stable isotope-labeled internal standard (SIL-IS) for bacterial RNA, which facilitates relative comparison of all modifications. While conventional SIL-IS approaches require the chemical synthesis of single modifications in weighable quantities, this SIL-IS consists of a nucleoside mixture covering all detectable RNA modifications of Escherichia coli, yet in small and initially unknown quantities. For absolute in addition to relative quantification, those quantities were determined by a combination of external calibration and sample spiking of the biosynthetic SIL-IS. For each nucleoside, we thus obtained a very robust relative response factor, which permits direct conversion of the MS signal to absolute amounts of substance. The application of the validated SIL-IS allowed highly precise quantification with standard deviations <2% during a 12-week period, and a linear dynamic range that was extended by two orders of magnitude. PMID:25129236

  6. Asymmetric Multiclass Traffic Assignment: a coherent formulation

    E-print Network

    Toint, Philippe

    Asymmetric Multiclass Traffic Assignment: a coherent formulation by Ph.L. Toint 1 and L. Wynter 2 Arceuil, France, EU Email: laura@inrets.fr Keywords: Asymmetric traffic assignment, multi­user class model, traffic equilibrium, multiclass cost functions. #12; Asymmetric Multiclass Traffic Assignment: A coherent

  7. Somatic synthesis Dendritic synthesis

    E-print Network

    Schuman, Erin M.

    Spine apparatus Polysome RNP Kinesin Protein synthesis machinery mRNA transport Turnover of local protein synthesis Impact of protein × synthesis Low High Neuron size and the benefits of localRNA deep sequencing · nanostring Synaptic input patterns Control of protein translation Protein synthesis

  8. Glycals in enantiospecific synthesis

    NASA Astrophysics Data System (ADS)

    Tolstikov, Alexander G.; Tolstikov, Genrikh A.

    1993-06-01

    The reactions of 1,2-unsaturated sugars (glycals) are considered in this review in relation to problems of the enantiospecific synthesis of natural products, their fragments, and their analogues. The reactions occurring both with retention of the heterocycle and those carried out with the aim of obtaining open chain chiral units are discussed. It is shown that the use of glycals as a stock of chiral substances which determine the configuration of the asymmetric centres in the target products of multistage synthesis is promising. Schemes for the synthesis of natural products of different types are considered: O- and C-glycosides, nucleosides, oligosaccharides, pheromones, antibiotics, toxins, glycosphingolipids, etc. The bibliography includes 161 references.

  9. Mechanistic insights on cooperative asymmetric multicatalysis using chiral counterions.

    PubMed

    Jindal, Garima; Sunoj, Raghavan B

    2014-08-15

    Cooperative multicatalytic methods are steadily gaining popularity in asymmetric catalysis. The use of chiral Brønsted acids such as phosphoric acids in conjunction with a range of transition metals has been proven to be effective in asymmetric synthesis. However, the lack of molecular-level understanding and the accompanying ambiguity on the role of the chiral species in stereoinduction continues to remain an unresolved puzzle. Herein, we intend to disclose some novel transition state models obtained through DFT(B3LYP and M06) computations for a quintessential reaction in this family, namely, palladium-catalyzed asymmetric Tsuji-Trost allylation of aldehydes. The aldehyde is activated as an enamine by the action of a secondary amine (organocatalysis), which then adds to an activated Pd-allylic species (transition metal catalysis) generated through the protonation of allyic alcohol by chiral BINOL-phosphoric acid (Brønsted acid catalysis). We aim to decipher the nature of chiral BINOL-phosphates and their role in creating a quaternary chiral carbon atom in this triple catalytic system. The study reports the first transition state model capable of rationalizing chiral counterion-induced enantioselectivity. It is found that the chiral phosphate acts as a counterion in the stereocontrolling event rather than the conventional ligand mode. PMID:25050786

  10. Efficient syntheses of korupensamines A, B and michellamine B by asymmetric Suzuki-Miyaura coupling reactions.

    PubMed

    Xu, Guangqing; Fu, Wenzhen; Liu, Guodu; Senanayake, Chris H; Tang, Wenjun

    2014-01-15

    Efficient asymmetric Suzuki-Miyaura coupling reactions are employed for the first time in total syntheses of chiral biaryl natural products korupensamine A and B in combination with an effective diastereoselective hydrogenation, allowing ultimately a concise and stereoselective synthesis of michellamine B. Chiral monophosphorus ligands L1-3 are effective for the syntheses of a series of functionalized chiral biaryls by asymmetric Suzuki-Miyaura coupling reactions in excellent yields and enantioselectivities (up to 99% ee). The presence of a polar-? interaction between the highly polarized BOP group and the extended ? system of arylboronic acid coupling partner is believed to be important for the high enantioselectivity. PMID:24147559

  11. Vanadium-Catalyzed Asymmetric Oxidation of r-Hydroxy Esters Using Molecular Oxygen as Stoichiometric Oxidant

    E-print Network

    Toste, Dean

    to effect the kinetic resolution of alcohols (eq 1).3 More recently, the palladium(II)/(-)-sparteine system in Organic Synthesis, Department of Chemistry, UniVersity of California, Berkeley, California 94720 Received November 4, 2004; E-mail: fdtoste@uclink.berkeley.edu Secondary alcohols of defined absolute stereochemical

  12. Asymmetric gold nanoparticle reduction into polydimethylsiloxane thin films

    NASA Astrophysics Data System (ADS)

    Dunklin, Jeremy R.; Forcherio, Gregory T.; Berry, Keith R.; Roper, D. Keith

    2014-09-01

    Polymer thin films embedded with plasmonic gold nanoparticles (AuNPs) are of significant interest in biomedicine, optics, photovoltaic, and nanoelectromechanical systems. Thin polydimethylsiloxane (PDMS) films containing 3-7 micron layers of AuNPs that were fabricated with a novel diffusive-reduction synthesis technique attenuated up to 85% of incoming laser light at the plasmon resonance. Rapid diffusive reduction of AuNPs into asymmetric PDMS thin films provided superior optothermal capabilities relative to thicker films in which AuNPs were reduced throughout. A photonto- heat conversion of up to 3000°C/watt was demonstrated, which represents a 3-230-fold increase over previous AuNPfunctionalized systems. Optical attenuation and thermal response increased in proportion to order of magnitude increases in tetrachloroaurate (TCA) solution concentration. Optical and thermoplasmonic responses were observed with and without an adjacent mesh support, which increased attenuation but decreased thermal response. Morphological, optical, and thermoplasmonic properties of asymmetric AuNP-PDMS films varied significantly with diffusive TCA concentration. Gold nanoparticles, networks, and conglomerates were formed via reduction as the amount of dissolved TCA increased across a log10-scale. Increasing TCA concentrations caused polymer surface cratering, leading to a larger effective surface area. This method, utilizing the diffusion of TCA into a single exposed partially cured PDMS interface, could be used to replace expensive lithographic or solution synthesis of plasmon-functionalized systems.

  13. Enantioselective Total Syntheses of (?)-Taiwaniaquinone H and (?)-Taiwaniaquinol B by Iridium-Catalyzed Borylation and Palladium-Catalyzed Asymmetric ?-Arylation

    PubMed Central

    Liao, Xuebin; Stanley, Levi M.; Hartwig, John F.

    2011-01-01

    We report a concise, enantioselective total synthesis of (?)-taiwaniaquinone H and the first enantioselective total synthesis of (?)-taiwaniaquinol B by a route that includes enantioselective, palladium-catalyzed ?-arylation of a ketone with an aryl bromide that was generated by sterically controlled halogenation via iridium-catalyzed C–H borylation. This asymmetric ?-arylation creates the benzylic, quaternary stereogenic center present in the taiwaniaquinoids. The synthesis was completed efficiently by developing a Lewis acid-promoted cascade to construct the [6,5,6] tricyclic core of an intermediate common to the synthesis of a number of taiwaniaquinoids. Through the preparation of these compounds, we demonstrate the utility of constructing benzylic, quaternary, stereogenic centers, even those lacking a carbonyl group in the ?-position, by asymmetric ?-arylation. PMID:21268578

  14. Universal Cosmic Absolute and Modern Science

    NASA Astrophysics Data System (ADS)

    Kostro, Ludwik

    The official Sciences, especially all natural sciences, respect in their researches the principle of methodic naturalism i.e. they consider all phenomena as entirely natural and therefore in their scientific explanations they do never adduce or cite supernatural entities and forces. The purpose of this paper is to show that Modern Science has its own self-existent, self-acting, and self-sufficient Natural All-in Being or Omni-Being i.e. the entire Nature as a Whole that justifies the scientific methodic naturalism. Since this Natural All-in Being is one and only It should be considered as the own scientifically justified Natural Absolute of Science and should be called, in my opinion, the Universal Cosmic Absolute of Modern Science. It will be also shown that the Universal Cosmic Absolute is ontologically enormously stratified and is in its ultimate i.e. in its most fundamental stratum trans-reistic and trans-personal. It means that in its basic stratum. It is neither a Thing or a Person although It contains in Itself all things and persons with all other sentient and conscious individuals as well, On the turn of the 20th century the Science has begun to look for a theory of everything, for a final theory, for a master theory. In my opinion the natural Universal Cosmic Absolute will constitute in such a theory the radical all penetrating Ultimate Basic Reality and will substitute step by step the traditional supernatural personal Absolute.

  15. Asymmetric information and macroeconomic dynamics

    NASA Astrophysics Data System (ADS)

    Hawkins, Raymond J.; Aoki, Masanao; Roy Frieden, B.

    2010-09-01

    We show how macroeconomic dynamics can be derived from asymmetric information. As an illustration of the utility of this approach we derive the equilibrium density, non-equilibrium densities and the equation of motion for the response to a demand shock for productivity in a simple economy. Novel consequences of this approach include a natural incorporation of time dependence into macroeconomics and a common information-theoretic basis for economics and other fields seeking to link micro-dynamics and macro-observables.

  16. Asymmetric Skyrmion lattice in helimagnets

    E-print Network

    Anjan Kundu

    2015-10-20

    Intricate spin textures in helimagnets, identified as stable topological Skyrmions, were observed experimentally, where Skyrme lattice was supposed to exhibit symmetric structures in the ground state. We show the possibility of asymmetric Skyrmions in a helimagnetic model, for individual Skyrmion as well as for the hexagonal Skyrme crystal with higher charge, as perturbative deformation and stabilization of exact ferromagnetic solitons. Such nonsymmetric configurations for the Skyrme lattice, predicted here theoretically, need to be verified in precision experiments.

  17. Asymmetric Skyrmion lattice in helimagnets

    E-print Network

    Kundu, Anjan

    2015-01-01

    Intricate spin textures in helimagnets, identified as stable topological Skyrmions, were observed experimentally, where Skyrme lattice was supposed to exhibit symmetric structures in the ground state. We show the possibility of asymmetric Skyrmions in a helimagnetic model, for individual Skyrmion as well as for the hexagonal Skyrme crystal with higher charge, as perturbative deformation and stabilization of exact ferromagnetic solitons. Such nonsymmetric configurations for the Skyrme lattice, predicted here theoretically, need to be verified in precision experiments.

  18. Asymmetric Wettability Directs Leidenfrost Droplets

    SciTech Connect

    Agapov, Rebecca L; Boreyko, Jonathan B; Briggs, Dayrl P; Srijanto, Bernadeta R; Retterer, Scott T; Collier, Pat; Lavrik, Nickolay V

    2014-01-01

    Leidenfrost phenomena on nano- and microstructured surfaces are of great importance for increasing control over heat transfer in high power density systems utilizing boiling phenomena. They also provide an elegant means to direct droplet motion in a variety of recently emerging fluidic systems. Here, we report the fabrication and characterization of tilted nanopillar arrays (TNPAs) that exhibit directional Leidenfrost water droplets under dynamic conditions, namely on impact with Weber numbers 40 at T 325 C. The batch fabrication of the TNPAs was achieved by glancing-angle anisotropic reactive ion etching of a thermally dewet platinum mask, with mean pillar diameters of 100 nm and heights of 200-500 nm. In contrast to previously implemented macro- and microscopic Leidenfrost ratchets, our TNPAs induce no preferential directional movement of Leidenfrost droplets under conditions approaching steady-state film boiling, suggesting that the observed droplet directionality is not a result of asymmetric vapor flow. Using high-speed imaging, phase diagrams were constructed for the boiling behavior upon impact for droplets falling onto TNPAs, straight nanopillar arrays, and smooth silicon surfaces. The asymmetric impact and directional trajectory of droplets was exclusive to the TNPAs for impacts corresponding to the transition boiling regime, revealing that asymmetric wettability upon impact is the mechanism for the droplet directionality.

  19. Asymmetric total syntheses of (+)- and (-)-versicolamide B and biosynthetic implications.

    PubMed

    Miller, Kenneth A; Tsukamoto, Sachiko; Williams, Robert M

    2009-04-01

    The Diels-Alder reaction is one of the most well-studied, synthetically useful organic transformations. While a significant number of naturally occurring substances are postulated to arise by biosynthetic Diels-Alder reactions, rigorous confirmation of a mechanistically distinct natural Diels-Alderase enzyme remains elusive. Within this context, several related fungi within the Aspergillus genus produce a number of metabolites of opposite absolute configuration including (+)- or (-)-versicolamide B. These alkaloids are hypothesized to arise via biosynthetic Diels-Alder reactions implying that each Aspergillus species possesses enantiomerically distinct Diels-Alderases. Herein, experimental validation of these biosynthetic proposals via deployment of the IMDA reaction as a key step in the asymmetric total syntheses of (+)- and (-)-versicolamide B is described. Laboratory validation of the proposed biosynthetic Diels-Alder construction, coupled with the secondary metabolite profile of the producing fungi, reveals that each Aspergillus species has evolved enantiomerically distinct indole oxidases, as well as enantiomerically distinct Diels-Alderases. PMID:20300443

  20. Comments on absolute and convective instabilities

    SciTech Connect

    Ram, A.K.; Bers, A.

    1992-01-24

    >Absolute or convective evolutions of instabilities can produce very different signatures of observed radiation from unstable plasmas. This is particularly useful in space plasmas when correlating experimentally observed emissions with theoretical models describing the source regions. A letter has questioned the basis and usefulness of the theory of absolute and convective instabilities by using some singular examples. The arguments put forth by these authors, based upon their singular examples, are misleading. Furthermore, the notion of a time-asymptotic limit is treated in an imprecise manner by these authors. Here, the authors point out the misconceptions in the arguments put forth by Oscarsson and Roennmark (1986) that question the validity and usefulness of the well-known theory of absolute and convective instabilities. The solid basis of the well-known theory is clarified.

  1. Absolute Distance Measurement with the MSTAR Sensor

    NASA Technical Reports Server (NTRS)

    Lay, Oliver P.; Dubovitsky, Serge; Peters, Robert; Burger, Johan; Ahn, Seh-Won; Steier, William H.; Fetterman, Harrold R.; Chang, Yian

    2003-01-01

    The MSTAR sensor (Modulation Sideband Technology for Absolute Ranging) is a new system for measuring absolute distance, capable of resolving the integer cycle ambiguity of standard interferometers, and making it possible to measure distance with sub-nanometer accuracy. The sensor uses a single laser in conjunction with fast phase modulators and low frequency detectors. We describe the design of the system - the principle of operation, the metrology source, beamlaunching optics, and signal processing - and show results for target distances up to 1 meter. We then demonstrate how the system can be scaled to kilometer-scale distances.

  2. Absolute Points for Multiple Assignment Problems

    ERIC Educational Resources Information Center

    Adlakha, V.; Kowalski, K.

    2006-01-01

    An algorithm is presented to solve multiple assignment problems in which a cost is incurred only when an assignment is made at a given cell. The proposed method recursively searches for single/group absolute points to identify cells that must be loaded in any optimal solution. Unlike other methods, the first solution is the optimal solution. The…

  3. The Absolute Normal Scores Test for Symmetry

    ERIC Educational Resources Information Center

    Penfield, Douglas A.; Sachdeva, Darshan

    1976-01-01

    The absolute normal scores test is described as a test for the symmetry of a distribution of scores about a location parameter. The test is compared to the sign test and the Wilcoxon test as an alternative to the "t"-test. (Editor/RK)

  4. On Relative and Absolute Conviction in Mathematics

    ERIC Educational Resources Information Center

    Weber, Keith; Mejia-Ramos, Juan Pablo

    2015-01-01

    Conviction is a central construct in mathematics education research on justification and proof. In this paper, we claim that it is important to distinguish between absolute conviction and relative conviction. We argue that researchers in mathematics education frequently have not done so and this has lead to researchers making unwarranted claims…

  5. Multiverse Set Theory and Absolutely Undecidable Propositions

    E-print Network

    Väänänen, Jouko

    Multiverse Set Theory and Absolutely Undecidable Propositions Jouko V¨a¨an¨anen University of Helsinki and University of Amsterdam Contents 1 Introduction 2 2 Background 4 3 The multiverse of sets 6 3.1 The one universe case . . . . . . . . . . . . . . . . . . . . . . . . 6 3.2 The multiverse

  6. Absolute partial photoionization cross sections of ozone.

    SciTech Connect

    Berkowitz, J.; Chemistry

    2008-04-01

    Despite the current concerns about ozone, absolute partial photoionization cross sections for this molecule in the vacuum ultraviolet (valence) region have been unavailable. By eclectic re-evaluation of old/new data and plausible assumptions, such cross sections have been assembled to fill this void.

  7. Absolute Time Radiometric Dating: the source

    E-print Network

    Kammer, Thomas

    Absolute Time Radiometric Dating: the source of the dates on the Geologic Time Scale #12;Radiometric Dating · Actually a simple technique. · Only two measurements are needed: · 1. The parent of parent and daughter elements. #12;Basis of the Technique · Radioactive elements "decay." Decay occurs

  8. General Relativity Requires Absolute Space and Time

    E-print Network

    Rainer W. Kuhne

    2002-09-30

    We examine two far-reaching and somewhat heretic consequences of General Relativity. (i) It requires a cosmology which includes a preferred rest frame, absolute space and time. (ii) A rotating universe and time travel are strict solutions of General Relativity.

  9. Teaching Absolute Value Inequalities to Mature Students

    ERIC Educational Resources Information Center

    Sierpinska, Anna; Bobos, Georgeana; Pruncut, Andreea

    2011-01-01

    This paper gives an account of a teaching experiment on absolute value inequalities, whose aim was to identify characteristics of an approach that would realize the potential of the topic to develop theoretical thinking in students enrolled in prerequisite mathematics courses at a large, urban North American university. The potential is…

  10. Absolute Differential Positronium-Formation Cross Sections

    NASA Astrophysics Data System (ADS)

    Shipman, M.; Armitage, S.; Beale, J.; Brawley, S. J.; Fayer, S. E.; Garner, A. J.; Leslie, D. E.; Van Reeth, P.; Laricchia, G.

    2015-07-01

    The first absolute experimental determinations of the differential cross sections for the formation of ground-state positronium are presented for He, Ar, H2 , and CO2 near 0°. Results are compared with available theories. The ratio of the differential and integrated cross sections for the targets exposes the higher propensity for forward emission of positronium formed from He and H2 .

  11. Computation in Dynamically Bounded Asymmetric Systems

    E-print Network

    Rutishauser, Ueli

    Previous explanations of computations performed by recurrent networks have focused on symmetrically connected saturating neurons and their convergence toward attractors. Here we analyze the behavior of asymmetrical connected ...

  12. Formal total synthesis of (+)-neopeltolide.

    PubMed

    Athe, Sudhakar; Chandrasekhar, Balla; Roy, Saumya; Pradhan, Tapan Kumar; Ghosh, Subhash

    2012-11-01

    This paper describes the formal total synthesis of (+)-neopeltolide, a cytotoxic macrolide isolated from the marine sponge Neopeltidae. The key features of the synthesis include an asymmetric Evans alkylation to fix the C9-methyl center, Jacobsen hydrolytic kinetic resolution of terminal epoxides followed by their regioselective opening to fix the stereocenters at the C11 and C13 positions, respectively, a Pd-catalyzed oxa-Michael reaction to construct the tetrahydropyran ring, and Yamaguchi macrolactonization to form the macrocyclic core of the molecule. PMID:23039136

  13. Total synthesis of herbimycin A.

    PubMed

    Yan, Rui; Bian, Chuancai; Yu, Xiaoming

    2014-06-20

    Benzoquinone ansamycin antibiotic herbimycin A was synthesized in 19 linear steps and 4.2% yield. Highlighted is the design of a chiral ?-lactone as the C11-C15 synthon that enabled a facile catalytic asymmetric synthesis of the challenging C8-C20 fragment of the target molecule. The easy access to the stereogenic centers and high overall yield made the strategy applicable in the molecular editing of benzoquinone ansamycins. PMID:24911938

  14. Dielectric response of asymmetric KNbO3/KTaO3 superlattices

    NASA Astrophysics Data System (ADS)

    Sigman, J.; Bae, H. J.; Norton, D. P.; Budai, J.; Boatner, L. A.

    2004-09-01

    The synthesis and properties of asymmetric KNbO3/KTaO3 superlattices is examined. Interdigitated electrodes are fabricated for temperature-dependent capacitance measurements. The nonlinear dielectric response of 1/N superlattice exhibits the anomalous positive tunability behavior indicative of antiferroelectricity. In contrast, the N/1 KNbO3/KTaO3 structures (N>1) appear to be either ferroelectric or paraelectric, depending on the temperature. Discussion of possible mechanisms for this behavior is given.

  15. Recent Developments in the Catalytic, Asymmetric Construction of Pyrroloindolines Bearing All-Carbon Quaternary Stereocenters

    PubMed Central

    Repka, Lindsay M.; Reisman, Sarah E.

    2014-01-01

    Pyrroloindoline alkaloids constitute a large family of natural products that has inspired the development of an impressive array of new reactions to prepare the key heterocyclic motif. This synopsis will address catalytic, asymmetric reactions developed to synthesize pyrroloindolines bearing C3a all-carbon quaternary stereocenters. The methods described herein include both transition metal-catalyzed and organocatalyzed reactions that have been demonstrated suitable for the synthesis of the pyrroloindoline framework. PMID:24295135

  16. Formal Asymmetric (4+1) Annulation Reaction between Sulfur Ylides and 1,3-Dienes.

    PubMed

    Rousseau, Olivier; Delaunay, Thierry; Dequirez, Geoffroy; Trieu-Van, Tran; Robeyns, Koen; Robiette, Raphaël

    2015-09-01

    A highly enantioselective synthesis of functionalized cyclopentanoids by a formal asymmetric (4+1) annulation strategy was developed. The methodology consists of a stereoselective cyclopropanation reaction between chiral sulfur ylides and 1,3-dienes followed by a, in situ, stereospecific MgI2 -catalyzed rearrangement of vinylcyclopropanes. This method is distinguished by a remarkable compatibility with functional groups and a high stereocontrol. PMID:26235566

  17. Enantioselective Synthesis of Tetrahydroprotoberberines and Bisbenzylisoquinoline Alkaloids from a Deprotonated -Aminonitrile

    E-print Network

    Lawson, Catherine L.

    Enantioselective Synthesis of Tetrahydroprotoberberines and Bisbenzylisoquinoline Alkaloids from for the preparation of various alkaloids. Here, the preparation of the benzylisoquinolines (+)-laudanidine and (-)-tetrahydropseudoepiberberine using Noyori's asymmetric transfer hydrogenation are described. The dimeric alkaloids (+)-O

  18. Total synthesis of (-)-?-kainic acid via chirality transfer through Ireland-Claisen rearrangement.

    PubMed

    Kesava Reddy, Naredla; Chandrasekhar, Srivari

    2013-04-01

    The total synthesis of (-)-?-Kainic acid is accomplished using a linear strategy involving Noyori asymmetric reduction and chirality transfer through Ireland-Claisen rearrangement as key steps. PMID:23470056

  19. Geometry-induced asymmetric diffusion

    E-print Network

    Robert S. Shaw; Norman Packard; Matthias Schröter; Harry L. Swinney

    2007-05-24

    Past work has shown that ions can pass through a membrane more readily in one direction than the other. We demonstrate here in a model and an experiment that for a mixture of small and large particles such asymmetric diffusion can arise solely from an asymmetry in the geometry of the pores of the membrane. Our deterministic simulation considers a two-dimensional gas of elastic disks of two sizes diffusing through a membrane, and our laboratory experiment examines the diffusion of glass beads of two sizes through a metal membrane. In both experiment and simulation, the membrane is permeable only to the smaller particles, and the asymmetric pores lead to an asymmetry in the diffusion rates of these particles. The presence of even a small percentage of large particles can clog a membrane, preventing passage of the small particles in one direction while permitting free flow of the small particles in the other direction. The purely geometric kinetic constraints may play a role in common biological contexts such as membrane ion channels.

  20. Robust control design with real parameter uncertainty using absolute stability theory. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    How, Jonathan P.; Hall, Steven R.

    1993-01-01

    The purpose of this thesis is to investigate an extension of mu theory for robust control design by considering systems with linear and nonlinear real parameter uncertainties. In the process, explicit connections are made between mixed mu and absolute stability theory. In particular, it is shown that the upper bounds for mixed mu are a generalization of results from absolute stability theory. Both state space and frequency domain criteria are developed for several nonlinearities and stability multipliers using the wealth of literature on absolute stability theory and the concepts of supply rates and storage functions. The state space conditions are expressed in terms of Riccati equations and parameter-dependent Lyapunov functions. For controller synthesis, these stability conditions are used to form an overbound of the H2 performance objective. A geometric interpretation of the equivalent frequency domain criteria in terms of off-axis circles clarifies the important role of the multiplier and shows that both the magnitude and phase of the uncertainty are considered. A numerical algorithm is developed to design robust controllers that minimize the bound on an H2 cost functional and satisfy an analysis test based on the Popov stability multiplier. The controller and multiplier coefficients are optimized simultaneously, which avoids the iteration and curve-fitting procedures required by the D-K procedure of mu synthesis. Several benchmark problems and experiments on the Middeck Active Control Experiment at M.I.T. demonstrate that these controllers achieve good robust performance and guaranteed stability bounds.

  1. The mechanism by which an asymmetric distribution of plant growth hormone is attained

    NASA Astrophysics Data System (ADS)

    Bandurski, Robert S.; Schulze, Aga; Jensen, Philip; Desrosiers, Mark; Epel, Bernard; Kowalczyk, Stanley

    Zea mays (sweet corn) seedlings attain an asymmetric distribution of the growth hormone indole-3-acetic acid (IAA) within 3 minutes following a gravity stimulus. Both free and esterified IAA (that is total IAA) accumulate to a greater extent in the lower half of the mesocotyl cortex of a horizontally placed seedling than in the upper half. Thus, changes in the ratio of free IAA to ester IAA cannot account for the asymmetric distribution. Our studies demonstrate there is no de novo synthesis of IAA in young seedlings. We conclude that asymmetric IAA distribution is attained by a gravity-induced, potential-regulated gating of the movement of IAA from kernel to shoot and from stele to cortex. As a working theory, which we call the Potential Gating Theory, we propose that perturbation of the plant's bioelectric field, induced by gravity, causes opening and closing of transport channels in the plasmodesmata connecting the vascular stele to the surrounding cortical tissues. This results in asymmetric growth hormone distribution which results in the asymmetric growth characteristic of the gravitropic response.

  2. Production of chiral alcohols from prochiral ketones by microalgal photo-biocatalytic asymmetric reduction reaction.

    PubMed

    Yang, Zhong-Hua; Luo, Li; Chang, Xu; Zhou, Wei; Chen, Geng-Hua; Zhao, Yan; Wang, Ya-Jun

    2012-06-01

    Microalgal photo-biocatalysis is a green technique for asymmetric synthesis. Asymmetric reduction of nonnatural prochiral ketones to produce chiral alcohols by microalgal photo-biocatalysis was studied in this work. Acetophenone (ACP) and ethyl acetoacetate (EAA) were chosen as model substrates for aromatic ketones and ?-ketoesters, respectively. Two prokaryotic cyanophyta and two eukaryotic chlorophyta were selected as photo-biocatalysts. The results proved that nonnatural prochiral ketones can be reduced by microalgal photo-biocatalysis with high enantioselectivity. Illumination is indispensable to the photo-biocatalysis. For aromatic ketone, cyanophyta are eligible biocatalysts. For ACP asymmetric reduction reaction, about 45% yield and 97% e.e. can be achieved by the photo-biocatalysis reaction with Spirulina platensis as biocatalyst. On the contrary, chlorophyta are efficient biocatalysts for ?-ketoester asymmetric reduction reaction among the four tested algae. For EAA asymmetric reduction reaction, about 70% yield and 90% e.e. can be achieved with Scenedesmus obliquus as biocatalyst. The microalgae used in this study outperformed other characterized biocatalysts such as microbial and plant cells. PMID:22322691

  3. Absolute plate motions by boundary velocity minimizations

    NASA Technical Reports Server (NTRS)

    Kaula, W. M.

    1975-01-01

    The main interaction of the earth's interior with the lithosphere is as a material source and sink. An absolute reference frame defined by minimizing the translational motion of tectonic plate boundaries differs by 0.6 cm/year from a frame defined by hot spot traces and by 0.4 cm/year from the frame defined by the most plausible model of drag forces on the plates. The rms absolute translational velocities are about 2 cm/year for ocean-ocean plate boundaries and 1.5 cm/year for ocean-continent plate boundaries. The close agreement between the source and sink and the drag-dependent definitions suggests that the lithosphere, as a stress guide, to some extent controls the locations of its sources and sinks.

  4. Absolute-magnitude distributions of supernovae

    SciTech Connect

    Richardson, Dean; Wright, John; Jenkins III, Robert L.; Maddox, Larry

    2014-05-01

    The absolute-magnitude distributions of seven supernova (SN) types are presented. The data used here were primarily taken from the Asiago Supernova Catalogue, but were supplemented with additional data. We accounted for both foreground and host-galaxy extinction. A bootstrap method is used to correct the samples for Malmquist bias. Separately, we generate volume-limited samples, restricted to events within 100 Mpc. We find that the superluminous events (M{sub B} < –21) make up only about 0.1% of all SNe in the bias-corrected sample. The subluminous events (M{sub B} > –15) make up about 3%. The normal Ia distribution was the brightest with a mean absolute blue magnitude of –19.25. The IIP distribution was the dimmest at –16.75.

  5. Asteroid absolute magnitudes and slope parameters

    NASA Technical Reports Server (NTRS)

    Tedesco, Edward F.

    1991-01-01

    A new listing of absolute magnitudes (H) and slope parameters (G) has been created and published in the Minor Planet Circulars; this same listing will appear in the 1992 Ephemerides of Minor Planets. Unlike previous listings, the values of the current list were derived from fits of data at the V band. All observations were reduced in the same fashion using, where appropriate, a single basis default value of 0.15 for the slope parameter. Distances and phase angles were computed for each observation. The data for 113 asteroids was of sufficiently high quality to permit derivation of their H and G. These improved absolute magnitudes and slope parameters will be used to deduce the most reliable bias-corrected asteroid size-frequency distribution yet made.

  6. From Hubble's NGSL to Absolute Fluxes

    NASA Technical Reports Server (NTRS)

    Heap, Sara R.; Lindler, Don

    2012-01-01

    Hubble's Next Generation Spectral Library (NGSL) consists of R-l000 spectra of 374 stars of assorted temperature, gravity, and metallicity. Each spectrum covers the wavelength range, 0.18-1.00 microns. The library can be viewed and/or downloaded from the website, http://archive.stsci.edu/prepds/stisngsll. Stars in the NGSL are now being used as absolute flux standards at ground-based observatories. However, the uncertainty in the absolute flux is about 2%, which does not meet the requirements of dark-energy surveys. We are therefore developing an observing procedure that should yield fluxes with uncertainties less than 1 % and will take part in an HST proposal to observe up to 15 stars using this new procedure.

  7. Absolute quantification method for protein concentration.

    PubMed

    Li, Mingdong; Tan, Jiaojie; Tarlov, Michael J; Zachariah, Michael R

    2014-12-16

    A fast and accurate assay to determine the absolute concentration of proteins is described based on direct measurement of droplet entrapped oligomer formation in electrospray. Here we demonstrate the approach using electrospray differential mobility analysis (ES-DMA), which can distinguish monomers and dimers from higher order oligomers. A key feature of the method is that it allows determination of the absolute number concentration of proteins eliminating the need for protein-specific calibration. The method was demonstrated by measuring the concentration of a NIST Standard Reference Material 927e (bovine serum albumin), a high-purity immunoglobulin G 1?, and a formulated Rituximab. The method may be applied to any electrospray source, regardless of diagnostic tool (e.g., MS or ion-mobility, etc.), provided the electrospray is operated in a droplet-fission mode. PMID:25412350

  8. Probing absolute spin polarization at the nanoscale.

    PubMed

    Eltschka, Matthias; Jäck, Berthold; Assig, Maximilian; Kondrashov, Oleg V; Skvortsov, Mikhail A; Etzkorn, Markus; Ast, Christian R; Kern, Klaus

    2014-12-10

    Probing absolute values of spin polarization at the nanoscale offers insight into the fundamental mechanisms of spin-dependent transport. Employing the Zeeman splitting in superconducting tips (Meservey-Tedrow-Fulde effect), we introduce a novel spin-polarized scanning tunneling microscopy that combines the probing capability of the absolute values of spin polarization with precise control at the atomic scale. We utilize our novel approach to measure the locally resolved spin polarization of magnetic Co nanoislands on Cu(111). We find that the spin polarization is enhanced by 65% when increasing the width of the tunnel barrier by only 2.3 Å due to the different decay of the electron orbitals into vacuum. PMID:25423049

  9. An absolute measure for a key currency

    NASA Astrophysics Data System (ADS)

    Oya, Shunsuke; Aihara, Kazuyuki; Hirata, Yoshito

    It is generally considered that the US dollar and the euro are the key currencies in the world and in Europe, respectively. However, there is no absolute general measure for a key currency. Here, we investigate the 24-hour periodicity of foreign exchange markets using a recurrence plot, and define an absolute measure for a key currency based on the strength of the periodicity. Moreover, we analyze the time evolution of this measure. The results show that the credibility of the US dollar has not decreased significantly since the Lehman shock, when the Lehman Brothers bankrupted and influenced the economic markets, and has increased even relatively better than that of the euro and that of the Japanese yen.

  10. Absolute and relative dosimetry for ELIMED

    SciTech Connect

    Cirrone, G. A. P.; Schillaci, F.; Scuderi, V.; Cuttone, G.; Candiano, G.; Musumarra, A.; Pisciotta, P.; Romano, F.; Carpinelli, M.; Presti, D. Lo; Raffaele, L.; Tramontana, A.; Cirio, R.; Sacchi, R.; Monaco, V.; Marchetto, F.; Giordanengo, S.

    2013-07-26

    The definition of detectors, methods and procedures for the absolute and relative dosimetry of laser-driven proton beams is a crucial step toward the clinical use of this new kind of beams. Hence, one of the ELIMED task, will be the definition of procedures aiming to obtain an absolute dose measure at the end of the transport beamline with an accuracy as close as possible to the one required for clinical applications (i.e. of the order of 5% or less). Relative dosimetry procedures must be established, as well: they are necessary in order to determine and verify the beam dose distributions and to monitor the beam fluence and the energetic spectra during irradiations. Radiochromic films, CR39, Faraday Cup, Secondary Emission Monitor (SEM) and transmission ionization chamber will be considered, designed and studied in order to perform a fully dosimetric characterization of the ELIMED proton beam.

  11. Relative errors can cue absolute visuomotor mappings.

    PubMed

    van Dam, Loes C J; Ernst, Marc O

    2015-12-01

    When repeatedly switching between two visuomotor mappings, e.g. in a reaching or pointing task, adaptation tends to speed up over time. That is, when the error in the feedback corresponds to a mapping switch, fast adaptation occurs. Yet, what is learned, the relative error or the absolute mappings? When switching between mappings, errors with a size corresponding to the relative difference between the mappings will occur more often than other large errors. Thus, we could learn to correct more for errors with this familiar size (Error Learning). On the other hand, it has been shown that the human visuomotor system can store several absolute visuomotor mappings (Mapping Learning) and can use associated contextual cues to retrieve them. Thus, when contextual information is present, no error feedback is needed to switch between mappings. Using a rapid pointing task, we investigated how these two types of learning may each contribute when repeatedly switching between mappings in the absence of task-irrelevant contextual cues. After training, we examined how participants changed their behaviour when a single error probe indicated either the often-experienced error (Error Learning) or one of the previously experienced absolute mappings (Mapping Learning). Results were consistent with Mapping Learning despite the relative nature of the error information in the feedback. This shows that errors in the feedback can have a double role in visuomotor behaviour: they drive the general adaptation process by making corrections possible on subsequent movements, as well as serve as contextual cues that can signal a learned absolute mapping. PMID:26280315

  12. The absolute spectrophotometric catalog by Anita Cochran

    NASA Astrophysics Data System (ADS)

    Burnashev, V. I.; Burnasheva, B. A.; Ruban, E. V.; Hagen-Torn, E. I.

    2014-06-01

    The absolute spectrophotometric catalog by Anita Cochran is presented in a machine-readable form. The catalog systematizes observations acquired at the McDonald Observatory in 1977-1978. The data are compared with other sources, in particular, the calculated broadband stellar magnitudes are compared with photometric observations by other authors, to show that the observational data given in the catalog are reliable and suitable for a variety of applications. Observations of variable stars of different types make Cochran's catalog especially valuable.

  13. Absolute photoionization cross sections of atomic oxygen

    NASA Technical Reports Server (NTRS)

    Samson, J. A. R.; Pareek, P. N.

    1982-01-01

    The absolute values of photoionization cross sections of atomic oxygen were measured from the ionization threshold to 120 A. An auto-ionizing resonance belonging to the 2S2P4(4P)3P(3Do, 3So) transition was observed at 479.43 A and another line at 389.97 A. The experimental data is in excellent agreement with rigorous close-coupling calculations that include electron correlations in both the initial and final states.

  14. Absolute Differential Positronium-Formation Cross Sections.

    PubMed

    Shipman, M; Armitage, S; Beale, J; Brawley, S J; Fayer, S E; Garner, A J; Leslie, D E; Van Reeth, P; Laricchia, G

    2015-07-17

    The first absolute experimental determinations of the differential cross sections for the formation of ground-state positronium are presented for He, Ar, H2, and CO2 near 0°. Results are compared with available theories. The ratio of the differential and integrated cross sections for the targets exposes the higher propensity for forward emission of positronium formed from He and H2. PMID:26230792

  15. cybersecurity.pnnl.gov Asymmetric Resilient Cybersecurity

    E-print Network

    cybersecurity.pnnl.gov Asymmetric Resilient Cybersecurity Cyber attacks are persistent Cyber attack have disastrous consequences on the rest of the system. The Asymmetric Resilient Cybersecurity altering how cybersecurity is implemented today. These capabilities will be driven by and measured by real

  16. Asymmetric visual deficit at high sustained Gz.

    PubMed

    Paul, M A

    1991-06-01

    Occasionally, acceleration research personnel see an individual who experiences consistent asymmetric visual deficits at high sustained Gz (HSG). Recently, one such centrifuge research subject from this laboratory was investigated with transcranial Doppler sonography. The results indicate an abnormal circle of Willis which could explain the asymmetric visual deficit at HSG. PMID:1859346

  17. Bulk electron temperature measurements using Asymmetric Triple

    E-print Network

    California at Los Angles, University of

    Bulk electron temperature measurements using Asymmetric Triple Langmuir probes Nevena Rakuljic electrons, and that another type of probe needs to be designed that would sample more dominant, bulk, electrons in the plasma. My project this summer has been to make an asymmetric triple probe that would allow

  18. Multipartite asymmetric quantum cloning S. Iblisdir,1

    E-print Network

    Cerf, Nicolas

    Multipartite asymmetric quantum cloning S. Iblisdir,1 A. Acín,2 N. J. Cerf,3 R. Filip,4 J. Fiurásek in asymmetric settings. We introduce cloning transformations that take N identical replicas of a pure state in any dimension as input and yield a collection of clones with nonidentical fidelities. As an example

  19. Defect-free ultrahigh flux asymmetric membranes

    DOEpatents

    Pinnau, Ingo (Austin, TX); Koros, William J. (Austin, TX)

    1990-01-01

    Defect-free, ultrahigh flux integrally-skinned asymmetric membranes having extremely thin surface layers (<0.2 .mu.m) comprised of glassy polymers are disclosed. The membranes are formed by casting an appropriate drope followed by forced convective evaporation of solvent to obtain a dry phase separated asymmetrical structure. The structure is then washed in a precipitation liquid and dried.

  20. Absolute dosimetry for extreme-ultraviolet lithography

    NASA Astrophysics Data System (ADS)

    Berger, Kurt W.; Campiotti, Richard H.

    2000-06-01

    The accurate measurement of an exposure dose reaching the wafer on an extreme ultraviolet (EUV) lithographic system has been a technical challenge directly applicable to the evaluation of candidate EUV resist materials and calculating lithography system throughputs. We have developed a dose monitoring sensor system that can directly measure EUV intensities at the wafer plane of a prototype EUV lithographic system. This sensor system, located on the wafer stage adjacent to the electrostatic chuck used to grip wafers, operates by translating the sensor into the aerial image, typically illuminating an 'open' (unpatterned) area on the reticle. The absolute signal strength can be related to energy density at the wafer, and thus used to determine resist sensitivity, and the signal as a function of position can be used to determine illumination uniformity at the wafer plane. Spectral filtering to enhance the detection of 13.4 nm radiation was incorporated into the sensor. Other critical design parameters include the packaging and amplification technologies required to place this device into the space and vacuum constraints of a EUV lithography environment. We describe two approaches used to determine the absolute calibration of this sensor. The first conventional approach requires separate characterization of each element of the sensor. A second novel approach uses x-ray emission from a mildly radioactive iron source to calibrate the absolute response of the entire sensor system (detector and electronics) in a single measurement.

  1. Catalytic asymmetric endo-selective [3+2] cycloaddition reactions of Schiff bases of ?-aminophosphonates with olefins using chiral metal amides.

    PubMed

    Yamashita, Yasuhiro; Nam, Liang Cheng; Dutton, Mark J; Yoshimoto, Susumu; Kobayashi, Sh?

    2015-12-14

    Catalytic asymmetric endo-selective [3+2] cycloaddition reactions of Schiff bases of ?-aminophosphonates with olefins are described. While the efficient asymmetric synthesis of several phosphonate analogues of proline derivatives is important in bioorganic chemistry, a direct catalytic method to prepare optically active endo [3+2] cycloadducts of ?-aminophosphonates with olefins has never been developed. We found for the first time that catalyst systems prepared from Group 11 metal amides with the (R)-FeSulphos ligand were effective for the asymmetric endo-selective [3+2] cycloaddition to afford the desired proline phosphonate analogues in high yields with high endo- and high enantioselectivities. PMID:26389539

  2. Asymmetric cancer cell division regulated by AKT.

    PubMed

    Dey-Guha, Ipsita; Wolfer, Anita; Yeh, Albert C; G Albeck, John; Darp, Revati; Leon, Eduardo; Wulfkuhle, Julia; Petricoin, Emanuel F; Wittner, Ben S; Ramaswamy, Sridhar

    2011-08-01

    Human tumors often contain slowly proliferating cancer cells that resist treatment, but we do not know precisely how these cells arise. We show that rapidly proliferating cancer cells can divide asymmetrically to produce slowly proliferating "G0-like" progeny that are enriched following chemotherapy in breast cancer patients. Asymmetric cancer cell division results from asymmetric suppression of AKT/PKB kinase signaling in one daughter cell during telophase of mitosis. Moreover, inhibition of AKT signaling with small-molecule drugs can induce asymmetric cancer cell division and the production of slow proliferators. Cancer cells therefore appear to continuously flux between symmetric and asymmetric division depending on the precise state of their AKT signaling network. This model may have significant implications for understanding how tumors grow, evade treatment, and recur. PMID:21757645

  3. Designing asymmetric multiferroics with strong magnetoelectric coupling

    NASA Astrophysics Data System (ADS)

    Lu, X. Z.; Xiang, H. J.

    2014-09-01

    Multiferroics offer exciting opportunities for electric-field control of magnetism. Single-phase multiferroics suitable for such applications at room temperature need much more study. Here, we propose the concept of an alternative type of multiferroics, namely, the "asymmetric multiferroic." In asymmetric multiferroics, two locally stable ferroelectric states are not symmetrically equivalent, leading to different magnetic properties between these two states. Furthermore, we predict from first principles that a Fe-Cr-Mo superlattice with the LiNbO3-type structure is such an asymmetric multiferroic. The strong ferrimagnetism, high ferroelectric polarization, and significant dependence of the magnetic transition temperature on polarization make this asymmetric multiferroic an ideal candidate for realizing electric-field control of magnetism at room temperature. Our study suggests that the asymmetric multiferroic may provide an alternative playground for voltage control of magnetism and find its applications in spintronics and quantum computing.

  4. Designing asymmetric multiferroics with strong magnetoelectric coupling

    NASA Astrophysics Data System (ADS)

    Lu, Xuezeng; Xiang, Hongjun; Rondinelli, James; Materials Theory; Design Group Team

    2015-03-01

    Multiferroics offer exciting opportunities for electric-field control of magnetism. Single-phase multiferroics suitable for such applications at room temperature need much more study. Here, we propose the concept of an alternative type of multiferroics, namely, the ``asymmetric multiferroic.'' In asymmetric multiferroics, two locally stable ferroelectric states are not symmetrically equivalent, leading to different magnetic properties between these two states. Furthermore, we predict from first principles that a Fe-Cr-Mo superlattice with the LiNbO3-type structure is such an asymmetric multiferroic. The strong ferrimagnetism, high ferroelectric polarization, and significant dependence of the magnetic transition temperature on polarization make this asymmetric multiferroic an ideal candidate for realizing electric-field control of magnetism at room temperature. Our study suggests that the asymmetric multiferroic may provide an alternative playground for voltage control of magnetism and find its applications in spintronics and quantum computing.

  5. Asymmetric cancer cell division regulated by AKT

    PubMed Central

    Dey-Guha, Ipsita; Wolfer, Anita; Yeh, Albert C.; G. Albeck, John; Darp, Revati; Leon, Eduardo; Wulfkuhle, Julia; Petricoin, Emanuel F.; Wittner, Ben S.; Ramaswamy, Sridhar

    2011-01-01

    Human tumors often contain slowly proliferating cancer cells that resist treatment, but we do not know precisely how these cells arise. We show that rapidly proliferating cancer cells can divide asymmetrically to produce slowly proliferating “G0-like” progeny that are enriched following chemotherapy in breast cancer patients. Asymmetric cancer cell division results from asymmetric suppression of AKT/PKB kinase signaling in one daughter cell during telophase of mitosis. Moreover, inhibition of AKT signaling with small-molecule drugs can induce asymmetric cancer cell division and the production of slow proliferators. Cancer cells therefore appear to continuously flux between symmetric and asymmetric division depending on the precise state of their AKT signaling network. This model may have significant implications for understanding how tumors grow, evade treatment, and recur. PMID:21757645

  6. Kinetic simulation of capacitively coupled plasmas driven by trapezoidal asymmetric voltage pulses

    SciTech Connect

    Diomede, Paola Economou, Demetre J.

    2014-06-21

    A kinetic Particle-In-Cell simulation with Monte Carlo Collisions was performed of a geometrically symmetric capacitively coupled, parallel-plate discharge in argon, driven by trapezoidal asymmetric voltage pulses with a period of 200?ns. The discharge was electrically asymmetric, making the ion energy distributions at the two electrodes different from one another. The fraction of the period (?), during which the voltage was kept at a constant (top-flat) positive value, was a critical control parameter. For the parameter range investigated, as ? increased, the mean ion energy on the grounded electrode increased and the ions became more directional, whereas the opposite was found for the ions striking the powered electrode. The absolute value of the DC self-bias voltage decreased as ? increased. Plasma instabilities, promoted by local double layers and electric field reversals during the time of the positive voltage excursion, were characterized by electron plasma waves launched from the sheath edge.

  7. Asymmetric Methods for the Synthesis of Flavanones, Chromanones, and Azaflavanones

    PubMed Central

    Nibbs, Antoinette E.

    2012-01-01

    Flavanones, chromanones, and related structures are privileged natural products that display a wide variety of biological activities. Although flavanoids are abundant in nature, there are a limited number of available general and efficient synthetic methods for accessing molecules of this class in a stereoselective manner. Their structurally simple architectures belie the difficulties involved in installation and maintenance of the stereogenic configuration at the C2 position, which can be sensitive and can undergo epimerization under mildly acidic, basic, and thermal reaction conditions. This review presents the methods currently used to access these related structures. The synthetic methods include manipulation of the flavone/flavanone core, carbon-carbon bond formation, and carbon–heteroatom bond formation. PMID:22876166

  8. Synthesis of Adjacent Quaternary Stereocenters by Catalytic Asymmetric Allylboration.

    PubMed

    Alam, Rauful; Vollgraff, Tobias; Eriksson, Lars; Szabó, Kálmán J

    2015-09-01

    Allylboration of ketones with ?-disubstituted allylboronic acids is performed in the presence of chiral BINOL derivatives. The reaction is suitable for single-step creation of adjacent quaternary stereocenters with high selectivity. We show that, with an appropriate choice of the chiral catalyst and the stereoisomeric prenyl substrate, full control of the stereo- and enantioselectivity is possible in the reaction. PMID:26316158

  9. Asymmetric synthesis of host-directed inhibitors of myxoviruses

    PubMed Central

    Moore, Terry W; Sana, Kasinath; Yan, Dan; Thepchatri, Pahk; Ndungu, John M; Saindane, Manohar T; Lockwood, Mark A; Natchus, Michael G; Liotta, Dennis C; Plemper, Richard K; Snyder, James P

    2013-01-01

    Summary High-throughput screening (HTS) previously identified benzimidazole 1 (JMN3-003) as a compound with broad antiviral activity against different influenza viruses and paramyxovirus strains. In pursuit of a lead compound from this series for development, we sought to increase both the potency and the aqueous solubility of 1. Lead optimization has achieved compounds with potent antiviral activity against a panel of myxovirus family members (EC50 values in the low nanomolar range) and much improved aqueous solubilities relative to that of 1. Additionally, we have devised a robust synthetic strategy for preparing 1 and congeners in an enantio-enriched fashion, which has allowed us to demonstrate that the (S)-enantiomers are generally 7- to 110-fold more potent than the corresponding (R)-isomers. PMID:23400228

  10. Absoluteness of Velocity Produced by Accelerating Process and Absolute Space-time Theory with Variable Scales

    E-print Network

    Mei Xiaochun

    2006-03-03

    It is proved by means of the dynamical effects of special relativity that velocity caused by accelerating process is not a relative concept. The influence of accelerating process should be considered in space-time theory. Besides the Newtonian absolute space-time theory with invariable space-time scales and the Einstein relative space-time theory with variable space-time scales, there exists the third space-time theory, i.e., the absolute space-time theory with variable space-time scales. At present, special relativity is divided into two parts, kinematics and dynamics. In kinematics, force and acceleration are not considered so that space and time becomes relative concepts. This division is completely artificial and irrational. The rational space-time theory should be established on the foundation of dynamics consistently. The changing rules of space, time and mass with speed should be dependent of accelerating processes and with absolute significance. The real meaning of invariability principle of high speed should be that we can not make the speed of an object speed with rest mass reach and exceed the speed of light in vacuum by the method of accelerating object. It is proved that the absolutely resting reference frame exists. In order to eliminate multifarious space-time paradoxes in special relativity, and coincide with Big-bang cosmology, the absolutely resting frame is necessary. A method is put forward to look for the absolutely resting reference frame. The isotropy reference frame of cosmic microwave background radiation can be regarded as the absolutely resting reference frame actually at present.

  11. Power spectra of a constrained totally asymmetric simple exclusion process

    NASA Astrophysics Data System (ADS)

    Cook, L. Jonathan; Zia, R. K. P.

    2010-07-01

    In nature, all biological systems function in a far-from-equilibrium state. Here, we study the process of translation in protein synthesis, using the totally asymmetric simple exclusion process (TASEP) as a model. In particular, we explore the effects of a finite supply of particles for the TASEP, as in a living cell with a finite pool of ribosomes. Specifically, we investigate the power spectrum associated with total occupancy, utilizing both Monte Carlo simulations and theoretical analysis. New features arise, such as large suppressions at low frequencies, due to the added constraint. A theory is formulated based on a Langevin approach with discrete space and time. With good agreement between the simulation and theory, we gain some insights into the effects of finite resources on the TASEP.

  12. Asymmetric exclusion process models for translation and biological transport

    NASA Astrophysics Data System (ADS)

    Shaw, Leah

    2005-03-01

    In the totally asymmetric simple exclusion process (TASEP), particles travel unidirectionally along a one-dimensional lattice and interact with each other by hard-core exclusion. Variants of the TASEP have been used to model the movement of molecular motors along biopolymers, including ribosomes on mRNA and various motors on cytoskeletal filaments. Ribosomes synthesize proteins as they traverse an mRNA molecule, so their motion is important in understanding the kinetics of protein production. We model protein synthesis as a TASEP with quenched disorder in the particle hopping rates. The hopping rates are determined by gene sequences and the availability of biomolecules. We use a statistical ensemble method in fitting the model to experimental data. The model is able to explain much of the nonlinear relationship between mRNA and protein levels.

  13. Condensation on Slippery Asymmetric Bumps

    E-print Network

    Park, Kyoo-Chul; He, Neil; Aizenberg, Joanna

    2015-01-01

    Bumps are omnipresent from human skin to the geological structures on planets, which offer distinct advantages in numerous phenomena including structural color, drag reduction, and extreme wettability. Although the topographical parameters of bumps such as radius of curvature of convex regions significantly influence various phenomena including anti-reflective structures and contact time of impacting droplets, the effect of the detailed bump topography on growth and transport of condensates have not been clearly understood. Inspired by the millimetric bumps of the Namib Desert beetle, here we report the identified role of radius of curvature and width of bumps with homogeneous surface wettability in growth rate, coalescence and transport of water droplets. Further rational design of asymmetric convex topography and synergetic combination with slippery coating simultaneously enable self-transport, leading to unseen five-fold higher growth rate and an order of magnitude faster shedding time of droplets compared...

  14. Organocatalytic cascade reactions as a new tool in total synthesis

    NASA Astrophysics Data System (ADS)

    Grondal, Christoph; Jeanty, Matthieu; Enders, Dieter

    2010-03-01

    The total synthesis of natural products and biologically active compounds, such as pharmaceuticals and agrochemicals, has reached an extraordinary level of sophistication. We are, however, still far away from the 'ideal synthesis' and the state of the art is still frequently hampered by lengthy protecting-group strategies and costly purification procedures derived from the step-by-step protocols. In recent years several new criteria have been brought forward to solve these problems and to improve total synthesis: atom, step and redox economy or protecting-group-free synthesis. Over the past decade the research area of organocatalysis has rapidly grown to become a third pillar of asymmetric catalysis standing next to metal and biocatalysis, thus paving the way for a new and powerful strategy that can help to address these issues - organocatalytic cascade reactions. In this Review we present the first applications of such asymmetric organocascade reactions to the total synthesis of natural products.

  15. Force on an Asymmetric Capacitor

    E-print Network

    Thomas B. Bahder; Chris Fazi

    2003-03-12

    When a high voltage (~30 kV) is applied to a capacitor whose electrodes have different physical dimensions, the capacitor experiences a net force toward the smaller electrode (Biefeld-Brown effect). We have verified this effect by building four capacitors of different shapes. The effect may have applications to vehicle propulsion and dielectric pumps. We review the history of this effect briefly through the history of patents by Thomas Townsend Brown. At present, the physical basis for the Biefeld-Brown effect is not understood. The order of magnitude of the net force on the asymmetric capacitor is estimated assuming two different mechanisms of charge conduction between its electrodes: ballistic ionic wind and ionic drift. The calculations indicate that ionic wind is at least three orders of magnitude too small to explain the magnitude of the observed force on the capacitor. The ionic drift transport assumption leads to the correct order of magnitude for the force, however, it is difficult to see how ionic drift enters into the theory. Finally, we present a detailed thermodynamic treatment of the net force on an asymmetric capacitor. In the future, to understand this effect, a detailed theoretical model must be constructed that takes into account plasma effects: ionization of gas (or air) in the high electric field region, charge transport, and resulting dynamic forces on the electrodes. The next series of experiments should determine whether the effect occurs in vacuum, and a careful study should be carried out to determine the dependence of the observed force on gas pressure, gas species and applied voltage.

  16. Hydrological effects on gravity measurements at the Canadian Absolute Gravity Site

    NASA Astrophysics Data System (ADS)

    Henton, J. A.; Liard, J. O.; Lambert, A.; Gagnon, C.; Courtier, N.

    2003-04-01

    The Canadian Gravity Standardization Net (CGSN), a network of primary and secondary gravity sites, provides the reference linkage for regional and local gravity surveys performed in different places and at different epochs in Canada. Maintained over the last five decades, CSGN has produced a reliable determination of the gravitational potential as well as associated temporal variations upon the Earth's surface. As part of CGSN more than 60 absolute gravity stations have been established across Canada. This network of absolute gravity sites is designed to provide absolute control for the CGSN and to continue the monitoring of temporal variations resulting from glacial isostatic adjustment, tectonic deformation and other processes. Additionally, monitoring of temporal gravity change rates at key, continuous GPS sites is an important step towards maintenance of an integrated reference system. The primary site for evaluating the stability of the absolute gravimeters for this network is the Canadian Absolute Gravity Site (CAGS), located near Ottawa at Cantley, Quebec (Lat. 45.585°N, Long. 75.807°W). CAGS is the base station for all JILA-2 and A10-003 field measurements as well as housing the Canadian Superconducting Gravimeter Installation (CSGI) which is contributing continuous data to the Global Geodynamics Project (1997-2003). Although owned by a consortium of Canadian universities, superconducting gravimeter GWR12 is operated with the assistance of the Geodetic Survey Division and provides a data stream which can be compared with frequent, repeated absolute gravity measurements. Additional CAGS/CSGI on-site data include: continuous water-level measurements from shallow (10m) and deep (120m) wells, observations from meteorological instrumentation, and continuous Global Positioning System (GPS) observations. Using the data available from the CAGS, we have begun to carry out a systematic self-consistent and complete synthesis, evaluation and interpretation of all available absolute gravity data collected over the last decade. Data from superconducting gravimeter GWR12, coupled with these absolute measurements, will be used to test models of seasonal variations in gravity at the CAGS base station due to groundwater effects identified in earlier work (e.g. Bower and Courtier, 1998).

  17. A wireless batch sealed absolute capacitive pressure sensor Orhan Akarb

    E-print Network

    Akin, Tayfun

    A wireless batch sealed absolute capacitive pressure sensor Orhan Akarb , Tayfun Akina,b,* , Khalil sensor; Sealed pressure sensor; Capacitive pressure sensor 1. Introduction Absolute pressure sensors- ricate absolute pressure sensors with sealed cavities that also allow easy lead transfer from inside

  18. Absolute versus convective instability of spiral waves Bjorn Sandstede

    E-print Network

    Scheel, Arnd

    Absolute versus convective instability of spiral waves Bjo¨rn Sandstede Department of Mathematics and convective instabilities of spirals are investigated using the continuous and the so-called absolute spectrum I, Freie Universita¨t Berlin, Arnimallee 2-6, 14195 Berlin, Germany Received 26 May 2000 Absolute

  19. Using, Seeing, Feeling, and Doing Absolute Value for Deeper Understanding

    ERIC Educational Resources Information Center

    Ponce, Gregorio A.

    2008-01-01

    Using sticky notes and number lines, a hands-on activity is shared that anchors initial student thinking about absolute value. The initial point of reference should help students successfully evaluate numeric problems involving absolute value. They should also be able to solve absolute value equations and inequalities that are typically found in…

  20. A Conceptual Approach to Absolute Value Equations and Inequalities

    ERIC Educational Resources Information Center

    Ellis, Mark W.; Bryson, Janet L.

    2011-01-01

    The absolute value learning objective in high school mathematics requires students to solve far more complex absolute value equations and inequalities. When absolute value problems become more complex, students often do not have sufficient conceptual understanding to make any sense of what is happening mathematically. The authors suggest that the…

  1. SYSTEM PERFORMANCE OF ABSOLUTE QUARTZ-CRYSTAL BAROMETERS WITH

    E-print Network

    Muschinski, Andreas

    SYSTEM PERFORMANCE OF ABSOLUTE QUARTZ-CRYSTAL BAROMETERS WITH SUB-MICROBAR PRECISION A Thesis 2009 All Rights Reserved #12;SYSTEM PERFORMANCE OF ABSOLUTE QUARTZ-CRYSTAL BAROMETERS WITH SUB OF ABSOLUTE QUARTZ-CRYSTAL BAROMETERS WITH SUB-MICROBAR PRECISION SEPTEMBER 2009 GANESH KUMAR SUBRAMANIAN

  2. Targeted CT Screening for Lung Cancer using Absolute Risk Prediction

    E-print Network

    Brent, Roger

    Targeted CT Screening for Lung Cancer using Absolute Risk Prediction Stephanie A. Kovalchik skovalch@rand.org FHCRC 2014 Risk Prediction Symposium June 11, 2014 1 #12;Outline · Lung Cancer Epidemiology and Screening · Screening Benefit and Absolute Risk · Absolute Risk Model for Lung Cancer

  3. Achieving Climate Change Absolute Accuracy in Orbit

    NASA Technical Reports Server (NTRS)

    Wielicki, Bruce A.; Young, D. F.; Mlynczak, M. G.; Thome, K. J; Leroy, S.; Corliss, J.; Anderson, J. G.; Ao, C. O.; Bantges, R.; Best, F.; Bowman, K.; Brindley, H.; Butler, J. J.; Collins, W.; Dykema, J. A.; Doelling, D. R.; Feldman, D. R.; Fox, N.; Huang, X.; Holz, R.; Huang, Y.; Jennings, D.; Jin, Z.; Johnson, D. G.; Jucks, K.; Kato, S.; Kratz, D. P.; Liu, X.; Lukashin, C.; Mannucci, A. J.; Phojanamongkolkij, N.; Roithmayr, C. M.; Sandford, S.; Taylor, P. C.; Xiong, X.

    2013-01-01

    The Climate Absolute Radiance and Refractivity Observatory (CLARREO) mission will provide a calibration laboratory in orbit for the purpose of accurately measuring and attributing climate change. CLARREO measurements establish new climate change benchmarks with high absolute radiometric accuracy and high statistical confidence across a wide range of essential climate variables. CLARREO's inherently high absolute accuracy will be verified and traceable on orbit to Système Internationale (SI) units. The benchmarks established by CLARREO will be critical for assessing changes in the Earth system and climate model predictive capabilities for decades into the future as society works to meet the challenge of optimizing strategies for mitigating and adapting to climate change. The CLARREO benchmarks are derived from measurements of the Earth's thermal infrared spectrum (5-50 micron), the spectrum of solar radiation reflected by the Earth and its atmosphere (320-2300 nm), and radio occultation refractivity from which accurate temperature profiles are derived. The mission has the ability to provide new spectral fingerprints of climate change, as well as to provide the first orbiting radiometer with accuracy sufficient to serve as the reference transfer standard for other space sensors, in essence serving as a "NIST [National Institute of Standards and Technology] in orbit." CLARREO will greatly improve the accuracy and relevance of a wide range of space-borne instruments for decadal climate change. Finally, CLARREO has developed new metrics and methods for determining the accuracy requirements of climate observations for a wide range of climate variables and uncertainty sources. These methods should be useful for improving our understanding of observing requirements for most climate change observations.

  4. Clock time is absolute and universal

    NASA Astrophysics Data System (ADS)

    Shen, Xinhang

    2015-09-01

    A critical error is found in the Special Theory of Relativity (STR): mixing up the concepts of the STR abstract time of a reference frame and the displayed time of a physical clock, which leads to use the properties of the abstract time to predict time dilation on physical clocks and all other physical processes. Actually, a clock can never directly measure the abstract time, but can only record the result of a physical process during a period of the abstract time such as the number of cycles of oscillation which is the multiplication of the abstract time and the frequency of oscillation. After Lorentz Transformation, the abstract time of a reference frame expands by a factor gamma, but the frequency of a clock decreases by the same factor gamma, and the resulting multiplication i.e. the displayed time of a moving clock remains unchanged. That is, the displayed time of any physical clock is an invariant of Lorentz Transformation. The Lorentz invariance of the displayed times of clocks can further prove within the framework of STR our earth based standard physical time is absolute, universal and independent of inertial reference frames as confirmed by both the physical fact of the universal synchronization of clocks on the GPS satellites and clocks on the earth, and the theoretical existence of the absolute and universal Galilean time in STR which has proved that time dilation and space contraction are pure illusions of STR. The existence of the absolute and universal time in STR has directly denied that the reference frame dependent abstract time of STR is the physical time, and therefore, STR is wrong and all its predictions can never happen in the physical world.

  5. Absolute Radiometric Calibration of EUNIS-06

    NASA Technical Reports Server (NTRS)

    Thomas, R. J.; Rabin, D. M.; Kent, B. J.; Paustian, W.

    2007-01-01

    The Extreme-Ultraviolet Normal-Incidence Spectrometer (EUNIS) is a soundingrocket payload that obtains imaged high-resolution spectra of individual solar features, providing information about the Sun's corona and upper transition region. Shortly after its successful initial flight last year, a complete end-to-end calibration was carried out to determine the instrument's absolute radiometric response over its Longwave bandpass of 300 - 370A. The measurements were done at the Rutherford-Appleton Laboratory (RAL) in England, using the same vacuum facility and EUV radiation source used in the pre-flight calibrations of both SOHO/CDS and Hinode/EIS, as well as in three post-flight calibrations of our SERTS sounding rocket payload, the precursor to EUNIS. The unique radiation source provided by the Physikalisch-Technische Bundesanstalt (PTB) had been calibrated to an absolute accuracy of 7% (l-sigma) at 12 wavelengths covering our bandpass directly against the Berlin electron storage ring BESSY, which is itself a primary radiometric source standard. Scans of the EUNIS aperture were made to determine the instrument's absolute spectral sensitivity to +- 25%, considering all sources of error, and demonstrate that EUNIS-06 was the most sensitive solar E W spectrometer yet flown. The results will be matched against prior calibrations which relied on combining measurements of individual optical components, and on comparisons with theoretically predicted 'insensitive' line ratios. Coordinated observations were made during the EUNIS-06 flight by SOHO/CDS and EIT that will allow re-calibrations of those instruments as well. In addition, future EUNIS flights will provide similar calibration updates for TRACE, Hinode/EIS, and STEREO/SECCHI/EUVI.

  6. An absolute radius scale for Saturn's rings

    NASA Technical Reports Server (NTRS)

    Nicholson, Philip D.; Cooke, Maren L.; Pelton, Emily

    1990-01-01

    Radio and stellar occultation observations of Saturn's rings made by the Voyager spacecraft are discussed. The data reveal systematic discrepancies of almost 10 km in some parts of the rings, limiting some of the investigations. A revised solution for Saturn's rotation pole has been proposed which removes the discrepancies between the stellar and radio occultation profiles. Corrections to previously published radii vary from -2 to -10 km for the radio occultation, and +5 to -6 km for the stellar occultation. An examination of spiral density waves in the outer A Ring supports that the revised absolute radii are in error by no more than 2 km.

  7. Absolute method of measuring magnetic susceptibility

    USGS Publications Warehouse

    Thorpe, A.; Senftle, F.E.

    1959-01-01

    An absolute method of standardization and measurement of the magnetic susceptibility of small samples is presented which can be applied to most techniques based on the Faraday method. The fact that the susceptibility is a function of the area under the curve of sample displacement versus distance of the magnet from the sample, offers a simple method of measuring the susceptibility without recourse to a standard sample. Typical results on a few substances are compared with reported values, and an error of less than 2% can be achieved. ?? 1959 The American Institute of Physics.

  8. Biomimetic total synthesis of (±)-doitunggarcinone A and (+)-garcibracteatone.

    PubMed

    Pepper, Henry P; Tulip, Stephen J; Nakano, Yuji; George, Jonathan H

    2014-03-21

    A full account of our oxidative radical cyclization approach to the synthesis of garcibracteatone and doitunggarcinone A is presented. This includes the first enantioselective synthesis of garcibracteatone, which allowed the absolute configuration of the natural compound to be determined. The first synthesis of doitunggarcinone A is also described, which confirms our reassignment of the relative configuration of this molecule. Novel syntheses of monoterpene fragments used to construct the target molecules are also reported. PMID:24575789

  9. Probing proton fluctuations with asymmetric rapidity correlations

    E-print Network

    Bzdak, Adam

    2015-01-01

    Intrinsic fluctuations of the proton saturation momentum generate asymmetric rapidity distributions on an event-by-event basis. We argue that the asymmetric component, $\\left$, of the orthogonal polynomial decomposition of the two-particle rapidity correlation function is a sensitive probe to this distribution of fluctuations. We present a simple model connecting the experimentally measured $\\left$ to the variance, $\\sigma$, of the distribution of the logarithm of the proton saturation scale. We find that $\\sigma\\approx 0. 5-1$ describes the asymmetric component of the rapidity correlations recently measured by the ATLAS collaboration.

  10. Asymmetric dark matter in braneworld cosmology

    SciTech Connect

    Meehan, Michael T.; Whittingham, Ian B. E-mail: Ian.Whittingham@jcu.edu.au

    2014-06-01

    We investigate the effect of a braneworld expansion era on the relic density of asymmetric dark matter. We find that the enhanced expansion rate in the early universe predicted by the Randall-Sundrum II (RSII) model leads to earlier particle freeze-out and an enhanced relic density. This effect has been observed previously by Okada and Seto (2004) for symmetric dark matter models and here we extend their results to the case of asymmetric dark matter. We also discuss the enhanced asymmetric annihilation rate in the braneworld scenario and its implications for indirect detection experiments.

  11. Regenerating a symmetry in asymmetric dark matter.

    PubMed

    Buckley, Matthew R; Profumo, Stefano

    2012-01-01

    Asymmetric dark matter theories generically allow for mass terms that lead to particle-antiparticle mixing. Over the age of the Universe, dark matter can thus oscillate from a purely asymmetric configuration into a symmetric mix of particles and antiparticles, allowing for pair-annihilation processes. Additionally, requiring efficient depletion of the primordial thermal (symmetric) component generically entails large annihilation rates. We show that unless some symmetry completely forbids dark matter particle-antiparticle mixing, asymmetric dark matter is effectively ruled out for a large range of masses, for almost any oscillation time scale shorter than the age of the Universe. PMID:22304253

  12. Measurement of the Absolute Branching Fraction of D0 to K- pi+

    SciTech Connect

    Aubert, B.; Bona, M.; Boutigny, D.; Karyotakis, Y.; Lees, J.P.; Poireau, V.; Prudent, X.; Tisserand, V.; Zghiche, A.; Garra Tico, J.; Grauges, E.; Lopez, L.; Palano, A.; Eigen, G.; Ofte, I.; Stugu, B.; Sun, L.; Abrams, G.S.; Battaglia, M.; Brown, D.N.; Button-Shafer, J.; /LBL, Berkeley /Birmingham U. /Ruhr U., Bochum /Bristol U. /British Columbia U. /Brunel U. /Novosibirsk, IYF /UC, Irvine /UCLA /UC, Riverside /UC, San Diego /UC, Santa Barbara /UC, Santa Cruz /Caltech /Cincinnati U. /Colorado U. /Colorado State U. /Dortmund U. /Munich, Tech. U. /Ecole Polytechnique /Edinburgh U. /Ferrara U. /Frascati /Genoa U. /Harvard U. /Heidelberg U. /Imperial Coll., London /Iowa U. /Iowa State U. /Johns Hopkins U. /Karlsruhe U. /Orsay, LAL /LLNL, Livermore /Liverpool U. /Queen Mary, U. of London /Royal Holloway, U. of London /Louisville U. /Manchester U. /Maryland U. /Massachusetts U., Amherst /MIT, LNS /McGill U. /Maryland U. /INFN, Milan /Mississippi U. /Montreal U. /Mt. Holyoke Coll. /Naples U. /NIKHEF, Amsterdam /Notre Dame U. /Ohio State U. /Oregon U. /Padua U. /Paris U., VI-VII /Pennsylvania U. /Perugia U. /Pisa U. /Prairie View A-M /Princeton U. /INFN, Rome /Rostock U. /Rutherford /DSM, DAPNIA, Saclay /South Carolina U. /SLAC /Stanford U., Phys. Dept. /SUNY, Albany /Tennessee U. /Texas U. /Texas U., Dallas /Turin U. /Trieste U. /Valencia U., IFIC /Victoria U. /Warwick U. /Wisconsin U., Madison /Yale U.

    2007-04-25

    The authors measure the absolute branching fraction for D{sup 0} {yields} K{sup -} {pi}{sup +} using partial reconstruction of {bar B}{sup 0} {yields} D*{sup +}X{ell}{sup -}{bar {nu}}{sub {ell}} decays, in which only the charged lepton and the pion from the decay D*{sup +} {yields} D{sup 0}{pi}{sup +} are used. Based on a data sample of 230 million B{bar B} pairs collected at the {Upsilon}(4S) resonance with the BABAR detector at the PEP-II asymmetric-energy B Factory at SLAC, they obtain {Beta}(D{sup 0} {yields} K{sup -}{pi}{sup +}) = (4.007 {+-} 0.037 {+-} 0.070)%, where the first error is statistical and the second error is systematic.

  13. Swarm's Absolute Scalar Magnetometers Burst Mode Results

    NASA Astrophysics Data System (ADS)

    Coisson, P.; Vigneron, P.; Hulot, G.; Crespo Grau, R.; Brocco, L.; Lalanne, X.; Sirol, O.; Leger, J. M.; Jager, T.; Bertrand, F.; Boness, A.; Fratter, I.

    2014-12-01

    Each of the three Swarm satellites embarks an Absolute Scalar Magnetometer (ASM) to provide absolute scalar measurements of the magnetic field with high accuracy and stability. Nominal data acquisition of these ASMs is 1 Hz. But they can also run in a so-called "burst mode" and provide data at 250 Hz. During the commissioning phase of the mission, seven burst mode acquisition campaigns have been run simultaneously for all satellites, obtaining a total of ten days of burs-mode data. These campaigns allowed the identification of issues related to the operations of the piezo-electric motor and the heaters connected to the ASM, that do not impact the nominal 1 Hz scalar data. We analyze the burst mode data to identify high frequency geomagnetic signals, focusing the analysis in two regions: the low latitudes, where we seek signatures of ionospheric irregularities, and the high latitudes, to identify high frequency signals related to polar region currents. Since these campaigns have been conducted during the initial months of the mission, the three satellites where still close to each other, allowing to analyze the spatial coherency of the signals. Wavelet analysis have revealed 31 Hz signals appearing in the night-side in the equatorial region.

  14. Experimental results for absolute cylindrical wavefront testing

    NASA Astrophysics Data System (ADS)

    Reardon, Patrick J.; Alatawi, Ayshah

    2014-09-01

    Applications for Cylindrical and near-cylindrical surfaces are ever-increasing. However, fabrication of high quality cylindrical surfaces is limited by the difficulty of accurate and affordable metrology. Absolute testing of such surfaces represents a challenge to the optical testing community as cylindrical reference wavefronts are difficult to produce. In this paper, preliminary results for a new method of absolute testing of cylindrical wavefronts are presented. The method is based on the merging of the random ball test method with the fiber optic reference test. The random ball test assumes a large number of interferograms of a good quality sphere with errors that are statistically distributed such that the average of the errors goes to zero. The fiber optic reference test utilizes a specially processed optical fiber to provide a clean high quality reference wave from an incident line focus from the cylindrical wave under test. By taking measurements at different rotation and translations of the fiber, an analogous procedure can be employed to determine the quality of the converging cylindrical wavefront with high accuracy. This paper presents and discusses the results of recent tests of this method using a null optic formed by a COTS cylindrical lens and a free-form polished corrector element.

  15. Absolute configuration of 7-epi-sesquithujene.

    PubMed

    Khrimian, Ashot; Cossé, Allard A; Crook, Damon J

    2011-06-24

    7-epi-sesquithujene (1) is a bicyclic sesquiterpene isolated from phoebe oil, an essential oil of the Brazilian walnut tree, Phoebe porosa. It is also produced by stressed ash trees and has been shown to elicit strong electrophysiological responses on emerald ash borer, Agrilus planipennis, antennae. In the course of the development of a synthetic 7-epi-sesquithujene lure for field testing against the emerald ash borer, we found that the absolute configuration of this compound had not been determined. We isolated >95% pure 7-epi-sesquithujene from phoebe oil via successive fractionation and conventional and argentation (HPLC) chromatographies. The specific optical rotation of this compound matched that of a synthetic product of known configuration. We also synthesized two other stereoisomers of sesquithujene and developed a chiral GC method to separate all four. Based on the specific rotation, stereoselective syntheses, and chiral GC analyses, 7-epi-sesquithujene present in phoebe oil and white ash was found to have the 2S,6S,7R absolute configuration. PMID:21574561

  16. A Divergent Synthesis of the ?13-9-Isofurans

    PubMed Central

    Taber, Douglass F.; Gu, Peiming; Li, Rui

    2009-01-01

    A stereodivergent total synthesis of the ?13-9-isofurans has been developed. The four core substituted tetrahydrofurans were prepared by the Sharpless asymmetric epoxidation and Sharpless asymmetric dihydroxylation followed by cascade cyclization. The relative configuration at C-8 was inverted by oxidation followed by immediate L-selectride reduction. The relative configuration of the C-15 diastereomers were assigned by (S)-Binol/LAH/EtOH reduction of the corresponding enone. This synthesis of the ?13-9-isofurans will provide sufficient material for further investigation of their biological activity. PMID:19572754

  17. Asymmetric Abelian Avalanches and Sandpiles Andrei Gabrielov

    E-print Network

    Gabrielov, Andrei

    Asymmetric Abelian Avalanches and Sandpiles Andrei Gabrielov Mathematical Sciences Institute consider two classes of threshold failure models, Abel- ian avalanches and sandpiles, with the redistribution matrices satisfying nat- ural conditions guaranteeing absence of infinite avalanches. We

  18. Asymmetric Cell Division: A Persistent Issue?

    E-print Network

    Laub, Michael T.

    Heterogeneity within a clonal population of cells can increase survival in the face of environmental stress. In a recent issue of Science, Aldridge et al. (2012) demonstrate that cell division in mycobacteria is asymmetric, ...

  19. Scheduling information broadcast in asymmetric environment 

    E-print Network

    Hameed, Sohail

    1997-01-01

    With the increasing popularity of portable wireless computers, mechanisms to efficiently transmit information to such clients are of significant interest. The environment under consideration is asymmetric in that the information server has...

  20. Asymmetric wave propagation in planar chiral fibers

    E-print Network

    Shemuly, Dana

    We demonstrate the realization of a two-dimensional chiral optical waveguide with an infinite translational symmetry that exhibits asymmetric wave propagation. The low-symmetry geometry of the cross-section that lacks any ...

  1. Investigation of asymmetric plasma blob dynamics

    E-print Network

    Soane, Alexander (Alexander Visotsky)

    2009-01-01

    The dynamics of asymmetric blobs is investigated in the Versatile Toroidal Facility (VTF) at MIT. Blobs are local regions of enhanced plasma density. Blobs are relevant to several areas of physics research, including fusion ...

  2. Chiral Brønsted Acids for Asymmetric Organocatalysis

    NASA Astrophysics Data System (ADS)

    Kampen, Daniela; Reisinger, Corinna M.; List, Benjamin

    Chiral Brønsted acid catalysis is an emerging area of organocatalysis. Since the pioneering studies of the groups of Akiyama and Terada in 2004 on the use of chiral BINOL phosphates as powerful Brønsted acid catalysts in asymmetric Mannich-type reactions, numerous catalytic asymmetric transformations involving imine activation have been realized by means of this catalyst class, including among others Friedel-Crafts, Pictet-Spengler, Strecker, cycloaddition reactions, transfer hydrogenations, and reductive aminations. More recently, chiral BINOL phosphates found application in multicomponent and cascade reactions as for example in an asymmetric version of the Biginelli reaction. With the introduction of chiral BINOL-derived N-triflyl phosphoramides in 2006, asymmetric Brønsted acid catalysis is no longer restricted to reactive substrates. Also certain carbonyl compounds can be activated through these stronger Brønsted acid catalysts. In dealing with sensitive substrate classes, chiral dicarboxylic acids proved of particular value.

  3. Sequential valuation networks for asymmetric decision problems

    E-print Network

    Demirer, Riza; Shenoy, Prakash P.

    2006-02-16

    This paper deals with representation and solution of asymmetric decision problems. We describe a new representation called sequential valuation networks that is a hybrid of Covaliu and Oliver’s sequential decision diagrams and Shenoy’s valuation...

  4. Sequential Valuation Networks for Asymmetric Decision Problems

    E-print Network

    Demirer, Riza; Shenoy, Prakash P.

    2001-01-01

    This paper deals with representation and solution of asymmetric decision problems. We describe a new representation called sequential valuation networks that is a hybrid of Covaliu and Oliver’s sequential decision diagrams and Shenoy’s valuation...

  5. Twin Higgs Asymmetric Dark Matter.

    PubMed

    García García, Isabel; Lasenby, Robert; March-Russell, John

    2015-09-18

    We study asymmetric dark matter (ADM) in the context of the minimal (fraternal) twin Higgs solution to the little hierarchy problem, with a twin sector with gauged SU(3)^{'}×SU(2)^{'}, a twin Higgs doublet, and only third-generation twin fermions. Naturalness requires the QCD^{'} scale ?_{QCD}^{'}?0.5-20??GeV, and that t^{'} is heavy. We focus on the light b^{'} quark regime, m_{b^{'}}??_{QCD}^{'}, where QCD^{'} is characterized by a single scale ?_{QCD}^{'} with no light pions. A twin baryon number asymmetry leads to a successful dark matter (DM) candidate: the spin-3/2 twin baryon, ?^{'}?b^{'}b^{'}b^{'}, with a dynamically determined mass (?5?_{QCD}^{'}) in the preferred range for the DM-to-baryon ratio ?_{DM}/?_{baryon}?5. Gauging the U(1)^{'} group leads to twin atoms (?^{'}-?^{'}[over ¯] bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo properties. Direct detection signatures satisfy current bounds, at times modified by dark form factors. PMID:26430985

  6. Lift production through asymmetric flapping

    NASA Astrophysics Data System (ADS)

    Jalikop, Shreyas; Sreenivas, K. R.

    2009-11-01

    At present, there is a strong interest in developing Micro Air Vehicles (MAV) for applications like disaster management and aerial surveys. At these small length scales, the flight of insects and small birds suggests that unsteady aerodynamics of flapping wings can offer many advantages over fixed wing flight, such as hovering-flight, high maneuverability and high lift at large angles of attack. Various lift generating mechanims such as delayed stall, wake capture and wing rotation contribute towards our understanding of insect flight. We address the effect of asymmetric flapping of wings on lift production. By visualising the flow around a pair of rectangular wings flapping in a water tank and numerically computing the flow using a discrete vortex method, we demonstrate that net lift can be produced by introducing an asymmetry in the upstroke-to-downstroke velocity profile of the flapping wings. The competition between generation of upstroke and downstroke tip vortices appears to hold the key to understanding this lift generation mechanism.

  7. Condensation on Slippery Asymmetric Bumps

    E-print Network

    Kyoo-Chul Park; Philseok Kim; Neil He; Joanna Aizenberg

    2015-01-14

    Bumps are omnipresent from human skin to the geological structures on planets, which offer distinct advantages in numerous phenomena including structural color, drag reduction, and extreme wettability. Although the topographical parameters of bumps such as radius of curvature of convex regions significantly influence various phenomena including anti-reflective structures and contact time of impacting droplets, the effect of the detailed bump topography on growth and transport of condensates have not been clearly understood. Inspired by the millimetric bumps of the Namib Desert beetle, here we report the identified role of radius of curvature and width of bumps with homogeneous surface wettability in growth rate, coalescence and transport of water droplets. Further rational design of asymmetric convex topography and synergetic combination with slippery coating simultaneously enable self-transport, leading to unseen five-fold higher growth rate and an order of magnitude faster shedding time of droplets compared to superhydrophobic surfaces. We envision that our fundamental understanding and innovative design of bumps can be applied to lead enhanced performance in various phase change applications including water harvesting.

  8. Twin Higgs Asymmetric Dark Matter

    E-print Network

    Isabel García García; Robert Lasenby; John March-Russell

    2015-09-16

    We study Asymmetric Dark Matter (ADM) in the context of the minimal (Fraternal) Twin Higgs solution to the little hierarchy problem, with a twin sector with gauged $SU(3)' \\times SU(2)'$, a twin Higgs, and only third generation twin fermions. Naturalness requires the QCD$^\\prime$ scale $\\Lambda'_{\\rm QCD} \\simeq 0.5 - 20 \\ {\\rm GeV}$, and $t'$ to be heavy. We focus on the light $b'$ quark regime, $m_{b'} \\lesssim \\Lambda'_{\\rm QCD}$, where QCD$^\\prime$ is characterised by a single scale $\\Lambda'_{\\rm QCD}$ with no light pions. A twin baryon number asymmetry leads to a successful DM candidate: the spin-3/2 twin baryon, $\\Delta' \\sim b'b'b'$, with a dynamically determined mass ($\\sim 5 \\Lambda'_{\\rm QCD}$) in the preferred range for the DM-to-baryon ratio $\\Omega_{\\rm DM}/\\Omega_{\\rm baryon} \\simeq 5$. Gauging the $U(1)'$ group leads to twin atoms ($\\Delta'$ - $\\bar {\\tau'}$ bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo properties. Direct detection signatures satisfy current bounds, at times modified by dark form factors.

  9. Twin Higgs Asymmetric Dark Matter

    NASA Astrophysics Data System (ADS)

    García García, Isabel; Lasenby, Robert; March-Russell, John

    2015-09-01

    We study asymmetric dark matter (ADM) in the context of the minimal (fraternal) twin Higgs solution to the little hierarchy problem, with a twin sector with gauged SU(3)'×SU(2)', atwin Higgs doublet, and only third-generation twin fermions. Naturalness requires the QCD' scale ?QCD'?0.5 - 20 GeV , and that t' is heavy. We focus on the light b' quark regime, mb'??QCD', where QCD' is characterized by a single scale ?QCD' with no light pions. A twin baryon number asymmetry leads to a successful dark matter (DM) candidate: the spin-3 /2 twin baryon, ?'˜b'b'b', with a dynamically determined mass (˜5 ?QCD') in the preferred range for the DM-to-baryon ratio ?DM/?baryon?5 . Gauging the U (1 )' group leads to twin atoms (?'-?' ¯ bound states) that are successful ADM candidates in significant regions of parameter space, sometimes with observable changes to DM halo properties. Direct detection signatures satisfy current bounds, at times modified by dark form factors.

  10. Tight focusing of an asymmetric Bessel beam

    NASA Astrophysics Data System (ADS)

    Kotlyar, Victor V.; Stafeev, Sergey S.; Porfirev, Alexey P.

    2015-12-01

    Tight focusing of a linearly polarized asymmetric Bessel beam, which has a topological charge n=3 and a crescent shape, was investigated numerically and experimentally. Using the Debye formulae, it was shown that the aplanatic lens of numerical aperture NA=0.9 forms a crescent in the focal plane. Experimentally, an asymmetric Bessel beam was formed by a spatial light modulator and focused by an immersive lens (NA=1.25). The crescent was also formed in the focal plane.

  11. A 3D finite element model for the vibration analysis of asymmetric rotating machines

    NASA Astrophysics Data System (ADS)

    Lazarus, A.; Prabel, B.; Combescure, D.

    2010-08-01

    This paper suggests a 3D finite element method based on the modal theory in order to analyse linear periodically time-varying systems. Presentation of the method is given through the particular case of asymmetric rotating machines. First, Hill governing equations of asymmetric rotating oscillators with two degrees of freedom are investigated. These differential equations with periodic coefficients are solved with classic Floquet theory leading to parametric quasimodes. These mathematical entities are found to have the same fundamental properties as classic eigenmodes, but contain several harmonics possibly responsible for parametric instabilities. Extension to the vibration analysis (stability, frequency spectrum) of asymmetric rotating machines with multiple degrees of freedom is achieved with a fully 3D finite element model including stator and rotor coupling. Due to Hill expansion, the usual degrees of freedom are duplicated and associated with the relevant harmonic of the Floquet solutions in the frequency domain. Parametric quasimodes as well as steady-state response of the whole system are ingeniously computed with a component-mode synthesis method. Finally, experimental investigations are performed on a test rig composed of an asymmetric rotor running on nonisotropic supports. Numerical and experimental results are compared to highlight the potential of the numerical method.

  12. Optical cryostat realizations at absolut System

    NASA Astrophysics Data System (ADS)

    Trollier, T.; Ravex, A.; Tanchon, J.

    2014-01-01

    This paper describes two kinds of optical cryostats designed and manufactured at Absolut System. The first one makes use of pressurized LN2 for temperature control of a sample holder in the 80 K - 470 K temperature range. An optical window is implemented above the sample holder to allow for rugosity and 3D distortion of heterogeneous semicon sample assemblies on a wafer. The second one makes use of CRYOMECH remote motor type pulse tube cryocoolers for temperature control of the sample holder in the 3 K - 300 K temperature range. In this type of cryostats, particular attention has been paid to reduce the vibrations exported by the cooler. These 4 K ultra low vibration cryostats are used for characterization of samples via optical windows. Both designs will be presented and the performance reported.

  13. Absolute image registration for geosynchronous satellites

    NASA Technical Reports Server (NTRS)

    Nankervis, R.; Koch, D.; Sielski, H.; Hall, D.

    1980-01-01

    A procedure for the absolute registration of earth images acquired by cameras on geosynchronous satellites is described. A conventional least squares process is used to estimate navigational parameters and camera pointing biases from observed minus computed landmark line and element numbers. These estimated parameters along with orbit and attitude dynamic models are used to register images, employing an automated grey-level correlation technique, inside the span represented by the landmark data. Experimental results obtained from processing the SMS-2 observation data base covering May 2, 1979 through May 20, 1979 show registration accuracies with a standard deviation of less than two pixels if the registration is within the landmark data span. It is also found that accurate registration can be expected for images obtained up to 48 hours outside of the landmark data span.

  14. Enhanced functional networks in absolute pitch

    PubMed Central

    Loui, Psyche; Zamm, Anna; Schlaug, Gottfried

    2013-01-01

    Functional networks in the human brain give rise to complex cognitive and perceptual abilities. While the decrease of functional connectivity is linked to neurological and psychiatric disorders, less is known about the consequences of increased functional connectivity. One population that has exceptionally enhanced perceptual abilities is people with absolute pitch (AP) — an ability to categorize tones into pitch classes without reference. AP has been linked to exceptional talent as well as to psychiatric and neurological conditions. Here we show that AP possessors have increased functional activation during music listening, as well as increased degrees, clustering, and local efficiency of functional correlations, with the difference being highest around the left superior temporal gyrus. Our results provide the first evidence that increased functional connectivity in a small-world brain network is related to exceptional perceptual abilities in a healthy population. PMID:22836173

  15. Towards absolute calibration of optical tweezers

    E-print Network

    Viana, N B; Mazolli, A; Mesquita, O N; Nussenzveig, H M; Rocha, M S

    2006-01-01

    Aiming at absolute force calibration of optical tweezers, following a critical review of proposed theoretical models, we present and test the results of MDSA (Mie-Debye-Spherical Aberration) theory, an extension of a previous (MD) model, taking account of spherical aberration at the glass/water interface. This first-principles theory is formulated entirely in terms of experimentally accessible parameters (none adjustable). Careful experimental tests of the MDSA theory, undertaken at two laboratories, with very different setups, are described. A detailed description is given of the procedures employed to measure laser beam waist, local beam power at the transparent microspheres trapped by the tweezers, microsphere radius and the trap transverse stiffness, as a function of radius and height in the (inverted microscope) sample chamber. We find generally very good agreement with MDSA theory predictions, for a wide size range, from the Rayleigh domain to large radii, including the values most often employed in pra...

  16. Micron Accurate Absolute Ranging System: Range Extension

    NASA Technical Reports Server (NTRS)

    Smalley, Larry L.; Smith, Kely L.

    1999-01-01

    The purpose of this research is to investigate Fresnel diffraction as a means of obtaining absolute distance measurements with micron or greater accuracy. It is believed that such a system would prove useful to the Next Generation Space Telescope (NGST) as a non-intrusive, non-contact measuring system for use with secondary concentrator station-keeping systems. The present research attempts to validate past experiments and develop ways to apply the phenomena of Fresnel diffraction to micron accurate measurement. This report discusses past research on the phenomena, and the basis of the use Fresnel diffraction distance metrology. The apparatus used in the recent investigations, experimental procedures used, preliminary results are discussed in detail. Continued research and equipment requirements on the extension of the effective range of the Fresnel diffraction systems is also described.

  17. MAGSAT: Vector magnetometer absolute sensor alignment determination

    NASA Technical Reports Server (NTRS)

    Acuna, M. H.

    1981-01-01

    A procedure is described for accurately determining the absolute alignment of the magnetic axes of a triaxial magnetometer sensor with respect to an external, fixed, reference coordinate system. The method does not require that the magnetic field vector orientation, as generated by a triaxial calibration coil system, be known to better than a few degrees from its true position, and minimizes the number of positions through which a sensor assembly must be rotated to obtain a solution. Computer simulations show that accuracies of better than 0.4 seconds of arc can be achieved under typical test conditions associated with existing magnetic test facilities. The basic approach is similar in nature to that presented by McPherron and Snare (1978) except that only three sensor positions are required and the system of equations to be solved is considerably simplified. Applications of the method to the case of the MAGSAT Vector Magnetometer are presented and the problems encountered discussed.

  18. Absolute measurements of fast neutrons using yttrium

    SciTech Connect

    Roshan, M. V.; Springham, S. V.; Rawat, R. S.; Lee, P.; Krishnan, M.

    2010-08-15

    Yttrium is presented as an absolute neutron detector for pulsed neutron sources. It has high sensitivity for detecting fast neutrons. Yttrium has the property of generating a monoenergetic secondary radiation in the form of a 909 keV gamma-ray caused by inelastic neutron interaction. It was calibrated numerically using MCNPX and does not need periodic recalibration. The total yttrium efficiency for detecting 2.45 MeV neutrons was determined to be f{sub n}{approx}4.1x10{sup -4} with an uncertainty of about 0.27%. The yttrium detector was employed in the NX2 plasma focus experiments and showed the neutron yield of the order of 10{sup 8} neutrons per discharge.

  19. Absolute nonlocality via distributed computing without communication

    NASA Astrophysics Data System (ADS)

    Czekaj, ?.; Paw?owski, M.; Vértesi, T.; Grudka, A.; Horodecki, M.; Horodecki, R.

    2015-09-01

    Understanding the role that quantum entanglement plays as a resource in various information processing tasks is one of the crucial goals of quantum information theory. Here we propose an alternative perspective for studying quantum entanglement: distributed computation of functions without communication between nodes. To formalize this approach, we propose identity games. Surprisingly, despite no signaling, we obtain that nonlocal quantum strategies beat classical ones in terms of winning probability for identity games originating from certain bipartite and multipartite functions. Moreover we show that, for a majority of functions, access to general nonsignaling resources boosts success probability two times in comparison to classical ones for a number of large enough outputs. Because there are no constraints on the inputs and no processing of the outputs in the identity games, they detect very strong types of correlations: absolute nonlocality.

  20. Total Synthesis of Sedum Alkaloids via Catalyst Controlled aza-Cope Rearrangement and Hydroformylation with Formaldehyde

    PubMed Central

    Ren, Hong; Wulff, William D.

    2013-01-01

    The catalytic asymmetric aminoallylation of chiral aldehydes is developed as a new method for the catalyst controlled synthesis of syn- and anti-1,3-aminoalcohols. This methodology is highlighted in the synthesis of the sedum alkaloids (+)-sedridine and (+)-allosedridine both of which have their final carbon incorporated during closure of the piperidine ring via a hydroformylation with formaldehyde. PMID:23259754

  1. Total synthesis of sedum alkaloids via catalyst controlled aza-Cope rearrangement and hydroformylation with formaldehyde.

    PubMed

    Ren, Hong; Wulff, William D

    2013-01-18

    The catalytic asymmetric aminoallylation of chiral aldehydes is developed as a new method for the catalyst controlled synthesis of syn- and anti-1,3-aminoalcohols. This methodology is highlighted in the synthesis of the sedum alkaloids (+)-sedridine and (+)-allosedridine both of which have their final carbon incorporated during closure of the piperidine ring via a hydroformylation with formaldehyde. PMID:23259754

  2. Application of cyclic phosphonamide reagents in the total synthesis of natural products and biologically active molecules

    PubMed Central

    Focken, Thilo

    2014-01-01

    Summary A review of the synthesis of natural products and bioactive compounds adopting phosphonamide anion technology is presented highlighting the utility of phosphonamide reagents in stereocontrolled bond-forming reactions. Methodologies utilizing phosphonamide anions in asymmetric alkylations, Michael additions, olefinations, and cyclopropanations will be summarized, as well as an overview of the synthesis of the employed phosphonamide reagents. PMID:25246946

  3. Total Synthesis of ?12-Prostaglandin J3, a Highly Potent and Selective Antileukemic Agent**

    PubMed Central

    Heretsch, Philipp; ElMarrouni, Abdelatif; Hale, Christopher R. H.; Pulukuri, Kiran K.; Kudva, Avinash K.; Narayan, Vivek; Sandeep Prabhu, K.

    2014-01-01

    A catalytic asymmetric total synthesis of the potent and selective antileukemic ?12-prostaglandin J3 (?12-PGJ3) is described. The convergent synthesis proceeded through intermediates 2 and 3, constructed enantioselectively from readily available starting materials and coupled through an aldol reaction followed by dehydration to afford stereoselectively the cyclopentenone alkylidene structural motif of the molecule. PMID:25098181

  4. Enantioselective synthesis of pladienolide B and truncated analogues as new anticancer agents.

    PubMed

    Kumar, Vemula Praveen; Chandrasekhar, Srivari

    2013-07-19

    An enantioselective synthesis of natural anticancer macrolide pladienolide B is described. The synthetic highlights include Sharpless asymmetric epoxidation, ring closing metathesis (RCM), Ireland-Claisen rearrangement, Shi epoxidation, and Pd-catalyzed Stille coupling as key steps. The synthetic route also allowed the synthesis of the truncated analogues (41a-d) of pladienolide B. PMID:23822896

  5. Relativistic Spacetime Based on Absolute Background

    E-print Network

    ChiYi Chen

    2015-09-19

    Based on the consideration of naturalness and physical facts in Einstein's theories of relativity, a nontrivial spacetime physical picture, which has a slight difference from the standard one, is introduced by making a further distinction on the absolute background of spacetime and the relative length or duration of base units of spacetime. In this picture, the coordinate base units in gravity-induced spacetime metric are defined by the standard clock and ruler equipped by the observer, and duplicated onto the every position of the whole universe. In contrast, the proper base units of spacetime in gravitational field are defined by the length and duration of physical events intervals in the same-type standard clock and ruler really located at every position of the universe. In principle, the reading number of the standard clock is counted by the undergone times of unit intervals defined depending on a certain kind of proper events. But the size of the base units of spacetime is essentially depicted by the length of the line segment, which is cut from the absolute background of spacetime by the proper events of unit interval. The effect of gravitation is just to change the length of this segment for base spacetime units. On the basis of such a physical picture of spacetime, in a fairly natural way we re-derive a new classical dynamical equation which satisfies a more realistic and moderately general principle of relativity. To further examine this physical picture including of gravitation and spacetime, we also reinterpret the gravitational redshifts for solar gravity tests.

  6. Measured and modelled absolute gravity in Greenland

    NASA Astrophysics Data System (ADS)

    Nielsen, E.; Forsberg, R.; Strykowski, G.

    2012-12-01

    Present day changes in the ice volume in glaciated areas like Greenland will change the load on the Earth and to this change the lithosphere will respond elastically. The Earth also responds to changes in the ice volume over a millennial time scale. This response is due to the viscous properties of the mantle and is known as Glaical Isostatic Adjustment (GIA). Both signals are present in GPS and absolute gravity (AG) measurements and they will give an uncertainty in mass balance estimates calculated from these data types. It is possible to separate the two signals if both gravity and Global Positioning System (GPS) time series are available. DTU Space acquired an A10 absolute gravimeter in 2008. One purpose of this instrument is to establish AG time series in Greenland and the first measurements were conducted in 2009. Since then are 18 different Greenland GPS Network (GNET) stations visited and six of these are visited more then once. The gravity signal consists of three signals; the elastic signal, the viscous signal and the direct attraction from the ice masses. All of these signals can be modelled using various techniques. The viscous signal is modelled by solving the Sea Level Equation with an appropriate ice history and Earth model. The free code SELEN is used for this. The elastic signal is modelled as a convolution of the elastic Greens function for gravity and a model of present day ice mass changes. The direct attraction is the same as the Newtonian attraction and is calculated as this. Here we will present the preliminary results of the AG measurements in Greenland. We will also present modelled estimates of the direct attraction, the elastic and the viscous signals.

  7. Vinylogous Esters and Amides: Useful Synthons for Diversity-Oriented and Natural Product Synthesis

    E-print Network

    Leighty, Matthew

    2009-05-04

    The first total synthesis of boehmeriasin A was achieved in seven steps from readily available materials with an overall yield of 29%. The absolute stereochemistry of the natural product was determined to be of the ...

  8. Absolute nuclear material assay using count distribution (LAMBDA) space

    DOEpatents

    Prasad, Mano K.; Snyderman, Neal J.; Rowland, Mark S.

    2015-12-01

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  9. Absolute nuclear material assay using count distribution (LAMBDA) space

    DOEpatents

    Prasad, Manoj K. (Pleasanton, CA); Snyderman, Neal J. (Berkeley, CA); Rowland, Mark S. (Alamo, CA)

    2012-06-05

    A method of absolute nuclear material assay of an unknown source comprising counting neutrons from the unknown source and providing an absolute nuclear material assay utilizing a model to optimally compare to the measured count distributions. In one embodiment, the step of providing an absolute nuclear material assay comprises utilizing a random sampling of analytically computed fission chain distributions to generate a continuous time-evolving sequence of event-counts by spreading the fission chain distribution in time.

  10. The asymmetric gait toenail unit sign.

    PubMed

    Zaias, Nardo; Rebell, Gerbert; Casal, German; Appel, Jason

    2012-01-01

    The aim of this investigation was to resolve a diagnostic problem and report toenail unit changes attributable to shoe friction that resemble onychomycosis, but that are fungus-negative, and identify common skeletal causes in patients with an asymmetric walking gait. X-ray and clinical feet inspections were performed to evaluate skeletal components that change normal foot biodynamics. Forty-nine patients, all dermatophyte-negative, were reviewed. All patients were those seen in our private practice who demonstrated skeletal and toenail unit abnormalities such as onycholysis, nail bed keratosis resembling distal subungual onychomycosis, nail plate surface abnormalities, distal toe skin keratosis, a diagnostic nail plate shape, as well as several skeletal abnormalities. The clinical abnormalities of the asymmetric gait syndrome include onycholysis, nail bed keratosis, nail plate surface abnormalities, and a diagnostic nail plate shape. By the patient's history, the skeletal findings that were present worsened with age and, in many patients, they were familial. Onychomycosis does not lead to an asymmetric gait nail problem, asymmetric gait toenail does not favor dermatophyte infection, and not all nail dystrophies are the result of an asymmetric walking gait. PMID:23008938

  11. Absolute and Convective Instability of a Liquid Jet

    NASA Technical Reports Server (NTRS)

    Lin, S. P.; Hudman, M.; Chen, J. N.

    1999-01-01

    The existence of absolute instability in a liquid jet has been predicted for some time. The disturbance grows in time and propagates both upstream and downstream in an absolutely unstable liquid jet. The image of absolute instability is captured in the NASA 2.2 sec drop tower and reported here. The transition from convective to absolute instability is observed experimentally. The experimental results are compared with the theoretical predictions on the transition Weber number as functions of the Reynolds number. The role of interfacial shear relative to all other relevant forces which cause the onset of jet breakup is explained.

  12. Gyrokinetic Statistical Absolute Equilibrium and Turbulence

    SciTech Connect

    Jian-Zhou Zhu and Gregory W. Hammett

    2011-01-10

    A paradigm based on the absolute equilibrium of Galerkin-truncated inviscid systems to aid in understanding turbulence [T.-D. Lee, "On some statistical properties of hydrodynamical and magnetohydrodynamical fields," Q. Appl. Math. 10, 69 (1952)] is taken to study gyrokinetic plasma turbulence: A finite set of Fourier modes of the collisionless gyrokinetic equations are kept and the statistical equilibria are calculated; possible implications for plasma turbulence in various situations are discussed. For the case of two spatial and one velocity dimension, in the calculation with discretization also of velocity v with N grid points (where N + 1 quantities are conserved, corresponding to an energy invariant and N entropy-related invariants), the negative temperature states, corresponding to the condensation of the generalized energy into the lowest modes, are found. This indicates a generic feature of inverse energy cascade. Comparisons are made with some classical results, such as those of Charney-Hasegawa-Mima in the cold-ion limit. There is a universal shape for statistical equilibrium of gyrokinetics in three spatial and two velocity dimensions with just one conserved quantity. Possible physical relevance to turbulence, such as ITG zonal flows, and to a critical balance hypothesis are also discussed.

  13. Towards absolute calibration of optical tweezers.

    PubMed

    Viana, N B; Rocha, M S; Mesquita, O N; Mazolli, A; Maia Neto, P A; Nussenzveig, H M

    2007-02-01

    Aiming at absolute force calibration of optical tweezers, following a critical review of proposed theoretical models, we present and test the results of Mie-Debye-spherical aberration (MDSA) theory, an extension of a previous (MD) model, taking account of spherical aberration at the glass-water interface. This first-principles theory is formulated entirely in terms of experimentally accessible parameters (none adjustable). Careful experimental tests of the MDSA theory, undertaken at two laboratories, with very different setups, are described. A detailed description is given of the procedures employed to measure laser beam waist, local beam power at the transparent microspheres trapped by the tweezers, microsphere radius, and the trap transverse stiffness, as a function of radius and height in the (inverted microscope) sample chamber. We find generally very good agreement with MDSA theory predictions, for a wide size range, from the Rayleigh domain to large radii, including the values most often employed in practice, and at different chamber heights, both with objective overfilling and underfilling. The results asymptotically approach geometrical optics in the mean over size intervals, as they should, and this already happens for size parameters not much larger than unity. MDSA predictions for the trapping threshold, position of stiffness peak, stiffness variation with height, multiple equilibrium points, and "hopping" effects among them are verified. Remaining discrepancies are ascribed to focus degradation, possibly arising from objective aberrations in the infrared, not yet included in MDSA theory. PMID:17358374

  14. Towards absolute calibration of optical tweezers

    NASA Astrophysics Data System (ADS)

    Viana, N. B.; Rocha, M. S.; Mesquita, O. N.; Mazolli, A.; Maia Neto, P. A.; Nussenzveig, H. M.

    2007-02-01

    Aiming at absolute force calibration of optical tweezers, following a critical review of proposed theoretical models, we present and test the results of Mie-Debye-spherical aberration (MDSA) theory, an extension of a previous (MD) model, taking account of spherical aberration at the glass-water interface. This first-principles theory is formulated entirely in terms of experimentally accessible parameters (none adjustable). Careful experimental tests of the MDSA theory, undertaken at two laboratories, with very different setups, are described. A detailed description is given of the procedures employed to measure laser beam waist, local beam power at the transparent microspheres trapped by the tweezers, microsphere radius, and the trap transverse stiffness, as a function of radius and height in the (inverted microscope) sample chamber. We find generally very good agreement with MDSA theory predictions, for a wide size range, from the Rayleigh domain to large radii, including the values most often employed in practice, and at different chamber heights, both with objective overfilling and underfilling. The results asymptotically approach geometrical optics in the mean over size intervals, as they should, and this already happens for size parameters not much larger than unity. MDSA predictions for the trapping threshold, position of stiffness peak, stiffness variation with height, multiple equilibrium points, and “hopping” effects among them are verified. Remaining discrepancies are ascribed to focus degradation, possibly arising from objective aberrations in the infrared, not yet included in MDSA theory.

  15. Elevation correction factor for absolute pressure measurements

    NASA Technical Reports Server (NTRS)

    Panek, Joseph W.; Sorrells, Mark R.

    1996-01-01

    With the arrival of highly accurate multi-port pressure measurement systems, conditions that previously did not affect overall system accuracy must now be scrutinized closely. Errors caused by elevation differences between pressure sensing elements and model pressure taps can be quantified and corrected. With multi-port pressure measurement systems, the sensing elements are connected to pressure taps that may be many feet away. The measurement system may be at a different elevation than the pressure taps due to laboratory space or test article constraints. This difference produces a pressure gradient that is inversely proportional to height within the interface tube. The pressure at the bottom of the tube will be higher than the pressure at the top due to the weight of the tube's column of air. Tubes with higher pressures will exhibit larger absolute errors due to the higher air density. The above effect is well documented but has generally been taken into account with large elevations only. With error analysis techniques, the loss in accuracy from elevation can be easily quantified. Correction factors can be applied to maintain the high accuracies of new pressure measurement systems.

  16. Absolute quantum energy inequalities in curved spacetime

    E-print Network

    Christopher J. Fewster; Calvin J. Smith

    2007-12-20

    Quantum Energy Inequalities (QEIs) are results which limit the extent to which the smeared renormalised energy density of the quantum field can be negative, when averaged along a timelike curve or over a more general timelike submanifold in spacetime. On globally hyperbolic spacetimes the minimally-coupled massive quantum Klein--Gordon field is known to obey a `difference' QEI that depends on a reference state chosen arbitrarily from the class of Hadamard states. In many spacetimes of interest this bound cannot be evaluated explicitly. In this paper we obtain the first `absolute' QEI for the minimally-coupled massive quantum Klein--Gordon field on four dimensional globally hyperbolic spacetimes; that is, a bound which depends only on the local geometry. The argument is an adaptation of that used to prove the difference QEI and utilises the Sobolev wave-front set to give a complete characterisation of the singularities of the Hadamard series. Moreover, the bound is explicit and can be formulated covariantly under additional (general) conditions. We also generalise our results to incorporate adiabatic states.

  17. Asymmetric Membrane Osmotic Capsules for Terbutaline Sulphate

    PubMed Central

    Gobade, N. G.; Koland, Marina; Harish, K. H.

    2012-01-01

    The aim of the present study was to design an asymmetric membrane capsule, an osmotic pump-based drug delivery system of ethyl cellulose for controlled release of terbutaline sulphate. asymmetric membrane capsules contains pore-forming water soluble additive, sorbitol in different concentrations in the capsule shell membrane, which after coming in contact with water, dissolves, resulting in an in situ formation of a microporous structure. The terbutaline sulphate is a ?-adrenoreceptor agonist widely used in the treatment of asthma. The oral dosage regimen of terbutaline sulphate is 5 mg twice or thrice daily, the plasma half-life is approximate 3-4 h and it produces GI irritation with extensive first pass metabolism. Hence, terbutaline sulphate was chosen as a model drug with an aim to develop controlled release system. Different formulations of ethyl cellulose were prepared by phase inversion technique using different concentrations of sorbitol as pore forming agent. It was found that the thickness of the prepared asymmetric membrane capsules was increased with increase in concentration of ethyl cellulose and pore forming agent, i.e. sorbitol. The dye release study in water and 10% sodium chloride solution indicates that, the asymmetric membrane capsules follow osmotic principle to release content. The pores formed due to sorbitol were confirmed by microscopic observation of transverse section of capsule membrane. Data of in vitro release study of terbutaline sulphate from asymmetric membrane capsules indicated that, the capsules prepared with 10% and 12.5% of ethyl cellulose and 25% of sorbitol released as much as 97.44% and 76.27% in 12 h, respectively with zero order release rate. Hence asymmetric membrane capsule of 10% ethyl cellulose and 25% of sorbitol is considered as optimum for controlled oral delivery of terbutaline sulphate. PMID:23204625

  18. Asymmetric membrane osmotic capsules for terbutaline sulphate.

    PubMed

    Gobade, N G; Koland, Marina; Harish, K H

    2012-01-01

    The aim of the present study was to design an asymmetric membrane capsule, an osmotic pump-based drug delivery system of ethyl cellulose for controlled release of terbutaline sulphate. asymmetric membrane capsules contains pore-forming water soluble additive, sorbitol in different concentrations in the capsule shell membrane, which after coming in contact with water, dissolves, resulting in an in situ formation of a microporous structure. The terbutaline sulphate is a ?-adrenoreceptor agonist widely used in the treatment of asthma. The oral dosage regimen of terbutaline sulphate is 5 mg twice or thrice daily, the plasma half-life is approximate 3-4 h and it produces GI irritation with extensive first pass metabolism. Hence, terbutaline sulphate was chosen as a model drug with an aim to develop controlled release system. Different formulations of ethyl cellulose were prepared by phase inversion technique using different concentrations of sorbitol as pore forming agent. It was found that the thickness of the prepared asymmetric membrane capsules was increased with increase in concentration of ethyl cellulose and pore forming agent, i.e. sorbitol. The dye release study in water and 10% sodium chloride solution indicates that, the asymmetric membrane capsules follow osmotic principle to release content. The pores formed due to sorbitol were confirmed by microscopic observation of transverse section of capsule membrane. Data of in vitro release study of terbutaline sulphate from asymmetric membrane capsules indicated that, the capsules prepared with 10% and 12.5% of ethyl cellulose and 25% of sorbitol released as much as 97.44% and 76.27% in 12 h, respectively with zero order release rate. Hence asymmetric membrane capsule of 10% ethyl cellulose and 25% of sorbitol is considered as optimum for controlled oral delivery of terbutaline sulphate. PMID:23204625

  19. Deep inelastic scattering on asymmetric nuclei

    E-print Network

    Saitô, K; Tsushima, K; Bissey, F; Afnan, I R; Thomas, A W

    2000-01-01

    We study deep inelastic scattering on isospin asymmetric nuclei. In particular, the difference of the nuclear structure functions and the Gottfried sum rule for the lightest mirror nuclei, 3He and 3H, are investigated. It is found that such systems can provide significant information on charge symmetry breaking and flavor asymmetry in the nuclear medium. Furthermore, we propose a new method to extract the neutron structure function from radioactive isotopes far from the line of stability. We also discuss the flavor asymmetry in the Drell-Yan process with isospin asymmetric nuclei.

  20. Deep inelastic scattering on asymmetric nuclei

    E-print Network

    K. Saito; C. Boros; K. Tsushima; F. Bissey; I. R. Afnan; A. W. Thomas

    2000-08-10

    We study deep inelastic scattering on isospin asymmetric nuclei. In particular, the difference of the nuclear structure functions and the Gottfried sum rule for the lightest mirror nuclei, 3He and 3H, are investigated. It is found that such systems can provide significant information on charge symmetry breaking and flavor asymmetry in the nuclear medium. Furthermore, we propose a new method to extract the neutron structure function from radioactive isotopes far from the line of stability. We also discuss the flavor asymmetry in the Drell-Yan process with isospin asymmetric nuclei.

  1. Asymmetric acoustic transmission in multiple frequency bands

    NASA Astrophysics Data System (ADS)

    Sun, Hong-xiang; Yuan, Shou-qi; Zhang, Shu-yi

    2015-11-01

    We report both experimentally and numerically that the multi-band device of the asymmetric acoustic transmission is realized by placing two periodic gratings with different periods on both sides of two brass plates immersed in water. The asymmetric acoustic transmission can exist in four frequency bands below 1500 kHz, which arises from the interaction between various diffractions from the two gratings and Lamb modes in the brass plates immersed in water. The results indicate that the device has the advantages of multiple band, broader bandwidth, and simpler structure. Our finding should have great potential applications in ultrasonic devices.

  2. The asymmetrically stepped, orifice compensated hydrostatic bearing

    NASA Astrophysics Data System (ADS)

    Scharrer, J. K.; Hibbs, R. I.; San Andres, L.

    1992-07-01

    An improved hydrostatic bedaring configuration consisting of a conventional orifice compensated, continuous, hydrostatic bearing augmented on one side by a ring with a smaller radial clearance is presented. Results for the leakage and rotordynamic coeffcients of this asymmetrically stepped hydrostatic bearing are calculated using a numerical solution of the film-average Navier-Stokes equations. Results of a parametric study on the effects of ring geometry and recess position on hydrostatic bearing performance are presented. The results show that the presence of the asymmetric step enhances the rotordynamic performance of an orifice compensated hydrostatic bearing.

  3. Relic abundance of asymmetric Dark Matter

    SciTech Connect

    Iminniyaz, Hoernisa; Drees, Manuel; Chen, Xuelei E-mail: drees@th.physik.uni-bonn.de

    2011-07-01

    We investigate the relic abundance of asymmetric Dark Matter particles that were in thermal equilibrium in the early universe. The standard analytic calculation of the symmetric Dark Matter is generalized to the asymmetric case. We calculate the asymmetry required to explain the observed Dark Matter relic abundance as a function of the annihilation cross section. We show that introducing an asymmetry always reduces the indirect detection signal from WIMP annihilation, although it has a larger annihilation cross section than symmetric Dark Matter. This opens new possibilities for the construction of realistic models of MeV Dark Matter.

  4. Hot and Flowing, Asymmetric Nuclear Matter

    NASA Astrophysics Data System (ADS)

    Marranghello, G. F.; Vasconcellos, C. A. Z.

    2001-04-01

    We develop a consistent treatment for hot and flowing asymmetric nuclear matter. Using the mean-field theory (MFT), predictions of the ? - ? Walecka model at finite temperature are compared with the corresponding results of the Zimanyi-Moszkowski and the non-linear models. The statistical theory of grand-canonical potentials is incorporated to the formalism. We also describe the behavior, at finite temperature, of the asymmetric and flowing nuclear matter. As an application, we describe bulk properties of neutron and protoneutron stars by considering the Tolman-Oppenheimer-Volkoff (TOV) equations.

  5. Total absorption in asymmetric hyperbolic media.

    PubMed

    Nefedov, Igor S; Valagiannopoulos, Constantinos A; Hashemi, Seed M; Nefedov, Evgeny I

    2013-01-01

    Finite-thickness slabs of hyperbolic media with tilted optical axes exhibit asymmetry properties for waves propagating upward and downward with respect to slab interfaces. Under certain conditions, asymmetric hyperbolic media acquire extreme permittivity parameters and the difference between upward and downward propagating waves becomes very large. Furthermore, both waves can be perfectly matched with the free space; such a feature makes possible the development of optically ultra thin perfect absorbers. The proposed approach is unified and allows the use of different -negative materials. Of particular interest is the asymmetric hyperbolic medium, made of silicon nanowires, since it can be directly applicable to solar cell systems. PMID:24036519

  6. Microscopic calculations in asymmetric nuclear matter

    E-print Network

    D. Alonso; F. Sammarruca

    2003-02-06

    A microscopic calculation of the equation of state for asymmetric nuclear matter is presented. We employ realistic nucleon-nucleon forces and operate within the Dirac-Brueckner-Hartree-Fock approach to nuclear matter. The focal point of this paper is a (momentum-space) G-matrix which properly accounts for the asymmetry between protons and neutrons. This will merge naturally into the development of an effective interaction suitable for applications to asymmetric nuclei, which will be the object of extensive study in the future.

  7. Total synthesis of heronapyrrole C.

    PubMed

    Ding, Xiao-Bo; Furkert, Daniel P; Capon, Robert J; Brimble, Margaret A

    2014-01-17

    A flexible total synthesis of the 2-nitropyrrole-derived marine natural product, (+)-heronapyrrole C, is reported. The approach is based on regioselective access to key building blocks containing the rare 4-substituted 2-nitropyrrole motif. Sharpless asymmetric epoxidation and dihydroxylation and a Shi epoxidation were used to introduce the five stereogenic centers of the bis-THF-diol side chain. The N-benzoyloxymethyl (Boz) protecting group was crucial for functionalization of the 2-nitropyrrole moiety and enabling final deprotection under mild conditions. PMID:24351092

  8. Competition between multiple totally asymmetric simple exclusion processes for a finite pool of resources

    NASA Astrophysics Data System (ADS)

    Cook, L. Jonathan; Zia, R. K. P.; Schmittmann, B.

    2009-09-01

    Using Monte Carlo simulations and a domain-wall theory, we discuss the effect of coupling several totally asymmetric simple exclusion processes (TASEPs) to a finite reservoir of particles. This simple model mimics directed biological transport processes in the presence of finite resources such as protein synthesis limited by a finite pool of ribosomes. If all TASEPs have equal length, we find behavior which is analogous to a single TASEP coupled to a finite pool. For the more generic case of chains with different lengths, several unanticipated regimes emerge. A generalized domain-wall theory captures our findings in good agreement with simulation results.

  9. Power Spectra of a Totally Asymmetric Simple Exclusion Process with Finite Resources

    NASA Astrophysics Data System (ADS)

    Cook, L. Jonathan; Zia, Royce K. P.

    2010-03-01

    In a cell, a mRNA has only a finite number of ribosomes to use during protein synthesis. We take this constraint into account in the modeling of translation by a totally asymmetric simple exclusion process (TASEP). Through Monte Carlo simulations and analytical methods, we study the power spectrum of the total particle occupancy of the TASEP. New features are found, such as a severe suppression at low frequencies. We formulate a theory based on a linearized Langevin equation with discrete space and time. With good agreement between the theoretical approach and the simulations, we gain some insight in how finite resources affect a TASEP.

  10. Asymmetric total syntheses of marine cyclic depsipeptide halipeptins A-D.

    PubMed

    Yu, Shouyun; Pan, Xianhua; Ma, Dawei

    2006-08-25

    Halipeptins A-D (1 a-d) are a family of natural cyclic depsipeptides isolated from marine sponges. Total syntheses of these four compounds are detailed in this report. The key elements in this synthesis include the elaboration of the polysubstituted decanoic acid parts by two asymmetric aldol reactions, assembly of the N-methyl-delta-hydroxyisoleucine residue by using either aza-Claisen rearrangement or methylation of aspartates as the key steps, and macrocyclization at the polysubstituted decanoic acid alanine site. PMID:16847995

  11. Asymmetric bioreduction of activated alkenes to industrially relevant optically active compounds

    PubMed Central

    Winkler, Christoph K.; Tasnádi, Gábor; Clay, Dorina; Hall, Mélanie; Faber, Kurt

    2012-01-01

    Ene-reductases from the ‘Old Yellow Enzyme’ family of flavoproteins catalyze the asymmetric reduction of various ?,?-unsaturated compounds at the expense of a nicotinamide cofactor. They have been applied to the synthesis of valuable enantiopure products, including chiral building blocks with broad industrial applications, terpenoids, amino acid derivatives and fragrances. The combination of these highly stereoselective biocatalysts with a cofactor recycling system has allowed the development of cost-effective methods for the generation of optically active molecules, which is strengthened by the availability of stereo-complementary enzyme homologues. PMID:22498437

  12. Easy To Synthesize, Robust Organo-osmium Asymmetric Transfer Hydrogenation Catalysts.

    PubMed

    Coverdale, James P C; Sanchez-Cano, Carlos; Clarkson, Guy J; Soni, Rina; Wills, Martin; Sadler, Peter J

    2015-05-26

    Asymmetric transfer hydrogenation (ATH) is an important process in organic synthesis for which the Noyori-type Ru(II) catalysts [(arene)Ru(Tsdiamine)] are now well established and widely used. We now demonstrate for the first time the catalytic activity of the osmium analogues. X-ray crystal structures of the 16-electron Os(II) catalysts are almost identical to those of Ru(II). Intriguingly the precursor complex was isolated as a dichlorido complex with a monodentate amine ligand. The Os(II) catalysts are readily synthesised (within 1?h) and exhibit excellent enantioselectivity in ATH reactions of ketones. PMID:25853228

  13. Stereodefined acyclic trisubstituted metal enolates towards the asymmetric formation of quaternary carbon stereocentres.

    PubMed

    Minko, Yury; Marek, Ilan

    2014-10-28

    Reactions that involve metal enolate species are amongst the most versatile carbon-carbon bond forming processes available to synthetic chemists. Enolate species are involved in a multitude of powerful applications in asymmetric organic synthesis, but the generation of fully substituted enolates in a geometrically defined form is not easily achieved especially in acyclic systems. In this Feature Article we focus on the most prominent examples reported in the literature describing the formation of highly diastereo- and enantiomerically enriched quaternary stereocentres in acyclic molecules derived from stereodefined non-cyclic trisubstituted metal enolates. PMID:25054432

  14. 4-Fluoro and 4-Hydroxy Pyrrolidine-thioxotetrahydropyrimidinones: Organocatalysts for Green Asymmetric Transformations in Brine.

    PubMed

    Kaplaneris, Nikolaos; Koutoulogenis, Giorgos; Raftopoulou, Marianna; Kokotos, Christoforos G

    2015-06-01

    The synthesis of both trans- and cis-diastereomers of pyrrolidinine-thioxotetrahydropyrimidinone bearing either a fluorine or a hydroxyl group was accomplished. The new compounds were tested for their catalytic properties in a variety of asymmetric organic transformations and compared with the first generation catalyst. It was found that the new catalysts could efficiently catalyze the reactions in brine, without the use of organic solvent, and by employing an almost stoichiometric amount of reagents. Thus, the products were isolated by simple extractions, avoiding the use of chromatography in excellent yields, diastereoselectivities, and enantioselectivities. PMID:25942500

  15. Niobium-mediated synthesis of phosphorus-rich molecules

    E-print Network

    Cossairt, Brandi M. (Brandi Michelle)

    2010-01-01

    The use of a sterically demanding enolate ligand -OC[2Ad]Mes supported by niobium has allowed for the synthesis of (Mes[2Ad]CO) 3Nb=PP7Nb(OC [2Ad]Mes)3 through P4 coupling by a low-valent niobium intermediate. This asymmetric ...

  16. Total synthesis of the proposed structure of astakolactin

    PubMed Central

    Mameda, Keisuke; Fujishiro, Moe; Yoshinaga, Yutaka

    2014-01-01

    Summary The first total synthesis of the proposed structure of astakolactin, a sesterterpene metabolite isolated from the marine sponge Cacospongia scalaris, has been achieved, mainly featuring Johnson–Claisen rearrangement, asymmetric Mukaiyama aldol reaction and MNBA-mediated lactonization. PMID:25383112

  17. Highly Efficient Synthesis of Chiral -Amino Acid Derivatives via

    E-print Network

    Zhang, Xumu

    Highly Efficient Synthesis of Chiral -Amino Acid Derivatives via Asymmetric Hydrogenation Wenjun-TangPhos complex is an efficient hydrogenation catalyst for making chiral -amino acid derivatives. With the Rh -amino acids has drawn a great deal of attention due to its importance in biomedical research

  18. Absolute detector quantum-efficiency measurements using correlated photons

    E-print Network

    Migdall, Alan

    metrologia Absolute detector quantum-efficiency measurements using correlated photons A. L. Migdall correlated photons for radiometric purposes has been set up at the National Institute of Standards and Technology (NIST). We use pairs of correlated photons to produce spatial maps of the absolute efficiency

  19. Absolute Humidity and the Seasonality of Influenza (Invited)

    NASA Astrophysics Data System (ADS)

    Shaman, J. L.; Pitzer, V.; Viboud, C.; Grenfell, B.; Goldstein, E.; Lipsitch, M.

    2010-12-01

    Much of the observed wintertime increase of mortality in temperate regions is attributed to seasonal influenza. A recent re-analysis of laboratory experiments indicates that absolute humidity strongly modulates the airborne survival and transmission of the influenza virus. Here we show that the onset of increased wintertime influenza-related mortality in the United States is associated with anomalously low absolute humidity levels during the prior weeks. We then use an epidemiological model, in which observed absolute humidity conditions temper influenza transmission rates, to successfully simulate the seasonal cycle of observed influenza-related mortality. The model results indicate that direct modulation of influenza transmissibility by absolute humidity alone is sufficient to produce this observed seasonality. These findings provide epidemiological support for the hypothesis that absolute humidity drives seasonal variations of influenza transmission in temperate regions. In addition, we show that variations of the basic and effective reproductive numbers for influenza, caused by seasonal changes in absolute humidity, are consistent with the general timing of pandemic influenza outbreaks observed for 2009 A/H1N1 in temperate regions. Indeed, absolute humidity conditions correctly identify the region of the United States vulnerable to a third, wintertime wave of pandemic influenza. These findings suggest that the timing of pandemic influenza outbreaks is controlled by a combination of absolute humidity conditions, levels of susceptibility and changes in population mixing and contact rates.

  20. Determination of Absolute Zero Using a Computer-Based Laboratory

    ERIC Educational Resources Information Center

    Amrani, D.

    2007-01-01

    We present a simple computer-based laboratory experiment for evaluating absolute zero in degrees Celsius, which can be performed in college and undergraduate physical sciences laboratory courses. With a computer, absolute zero apparatus can help demonstrators or students to observe the relationship between temperature and pressure and use…

  1. Absolute Plate Velocities from Seismic Anisotropy

    NASA Astrophysics Data System (ADS)

    Kreemer, Corné; Zheng, Lin; Gordon, Richard

    2015-04-01

    The orientation of seismic anisotropy inferred beneath plate interiors may provide a means to estimate the motions of the plate relative to the sub-asthenospheric mantle. Here we analyze two global sets of shear-wave splitting data, that of Kreemer [2009] and an updated and expanded data set, to estimate plate motions and to better understand the dispersion of the data, correlations in the errors, and their relation to plate speed. We also explore the effect of using geologically current plate velocities (i.e., the MORVEL set of angular velocities [DeMets et al. 2010]) compared with geodetically current plate velocities (i.e., the GSRM v1.2 angular velocities [Kreemer et al. 2014]). We demonstrate that the errors in plate motion azimuths inferred from shear-wave splitting beneath any one tectonic plate are correlated with the errors of other azimuths from the same plate. To account for these correlations, we adopt a two-tier analysis: First, find the pole of rotation and confidence limits for each plate individually. Second, solve for the best fit to these poles while constraining relative plate angular velocities to consistency with the MORVEL relative plate angular velocities. The SKS-MORVEL absolute plate angular velocities (based on the Kreemer [2009] data set) are determined from the poles from eight plates weighted proportionally to the root-mean-square velocity of each plate. SKS-MORVEL indicates that eight plates (Amur, Antarctica, Caribbean, Eurasia, Lwandle, Somalia, Sundaland, and Yangtze) have angular velocities that differ insignificantly from zero. The net rotation of the lithosphere is 0.25±0.11° Ma-1 (95% confidence limits) right-handed about 57.1°S, 68.6°E. The within-plate dispersion of seismic anisotropy for oceanic lithosphere (?=19.2° ) differs insignificantly from that for continental lithosphere (?=21.6° ). The between-plate dispersion, however, is significantly smaller for oceanic lithosphere (?=7.4° ) than for continental lithosphere (?=14.7° ). Two of the slowest-moving plates, Antarctica (vRMS=4 mm a-1, ?=29° ) and Eurasia (vRMS=3 mm a-1, ?=33° ), have two of the largest within-plate dispersions, which may indicate that a plate must move faster than ˜5 mm a-1 to result in seismic anisotropy useful for estimating plate motion. We will investigate if these relationships still hold with the new expanded data set and with the alternative set of relative plate angular velocities. We have found systematic differences between the SKS orientations and our predicted plate motion azimuths underneath the Arabia plate, which suggests to us either plate-scale mantle flow process not directly associated with that plate's absolute motion or intrinsic lithospheric anisotropy. We will discuss more of such discrepancies underneath other plates using the enlarged data set.

  2. Absolute determination of local tropospheric OH concentrations

    NASA Technical Reports Server (NTRS)

    Armerding, Wolfgang; Comes, Franz-Josef

    1994-01-01

    Long path absorption (LPA) according to Lambert Beer's law is a method to determine absolute concentrations of trace gases such as tropospheric OH. We have developed a LPA instrument which is based on a rapid tuning of the light source which is a frequency doubled dye laser. The laser is tuned across two or three OH absorption features around 308 nm with a scanning speed of 0.07 cm(exp -1)/microsecond and a repetition rate of 1.3 kHz. This high scanning speed greatly reduces the fluctuation of the light intensity caused by the atmosphere. To obtain the required high sensitivity the laser output power is additionally made constant and stabilized by an electro-optical modulator. The present sensitivity is of the order of a few times 10(exp 5) OH per cm(exp 3) for an acquisition time of a minute and an absorption path length of only 1200 meters so that a folding of the optical path in a multireflection cell was possible leading to a lateral dimension of the cell of a few meters. This allows local measurements to be made. Tropospheric measurements have been carried out in 1991 resulting in the determination of OH diurnal variation at specific days in late summer. Comparison with model calculations have been made. Interferences are mainly due to SO2 absorption. The problem of OH self generation in the multireflection cell is of minor extent. This could be shown by using different experimental methods. The minimum-maximum signal to noise ratio is about 8 x 10(exp -4) for a single scan. Due to the small size of the absorption cell the realization of an open air laboratory is possible in which by use of an additional UV light source or by additional fluxes of trace gases the chemistry can be changed under controlled conditions allowing kinetic studies of tropospheric photochemistry to be made in open air.

  3. Orion Absolute Navigation System Progress and Challenge

    NASA Technical Reports Server (NTRS)

    Holt, Greg N.; D'Souza, Christopher

    2012-01-01

    The absolute navigation design of NASA's Orion vehicle is described. It has undergone several iterations and modifications since its inception, and continues as a work-in-progress. This paper seeks to benchmark the current state of the design and some of the rationale and analysis behind it. There are specific challenges to address when preparing a timely and effective design for the Exploration Flight Test (EFT-1), while still looking ahead and providing software extensibility for future exploration missions. The primary onboard measurements in a Near-Earth or Mid-Earth environment consist of GPS pseudo-range and delta-range, but for future explorations missions the use of star-tracker and optical navigation sources need to be considered. Discussions are presented for state size and composition, processing techniques, and consider states. A presentation is given for the processing technique using the computationally stable and robust UDU formulation with an Agee-Turner Rank-One update. This allows for computational savings when dealing with many parameters which are modeled as slowly varying Gauss-Markov processes. Preliminary analysis shows up to a 50% reduction in computation versus a more traditional formulation. Several state elements are discussed and evaluated, including position, velocity, attitude, clock bias/drift, and GPS measurement biases in addition to bias, scale factor, misalignment, and non-orthogonalities of the accelerometers and gyroscopes. Another consideration is the initialization of the EKF in various scenarios. Scenarios such as single-event upset, ground command, and cold start are discussed as are strategies for whole and partial state updates as well as covariance considerations. Strategies are given for dealing with latent measurements and high-rate propagation using multi-rate architecture. The details of the rate groups and the data ow between the elements is discussed and evaluated.

  4. Evaluation of the Absolute Regional Temperature Potential

    NASA Technical Reports Server (NTRS)

    Shindell, D. T.

    2012-01-01

    The Absolute Regional Temperature Potential (ARTP) is one of the few climate metrics that provides estimates of impacts at a sub-global scale. The ARTP presented here gives the time-dependent temperature response in four latitude bands (90-28degS, 28degS-28degN, 28-60degN and 60-90degN) as a function of emissions based on the forcing in those bands caused by the emissions. It is based on a large set of simulations performed with a single atmosphere-ocean climate model to derive regional forcing/response relationships. Here I evaluate the robustness of those relationships using the forcing/response portion of the ARTP to estimate regional temperature responses to the historic aerosol forcing in three independent climate models. These ARTP results are in good accord with the actual responses in those models. Nearly all ARTP estimates fall within +/-20%of the actual responses, though there are some exceptions for 90-28degS and the Arctic, and in the latter the ARTP may vary with forcing agent. However, for the tropics and the Northern Hemisphere mid-latitudes in particular, the +/-20% range appears to be roughly consistent with the 95% confidence interval. Land areas within these two bands respond 39-45% and 9-39% more than the latitude band as a whole. The ARTP, presented here in a slightly revised form, thus appears to provide a relatively robust estimate for the responses of large-scale latitude bands and land areas within those bands to inhomogeneous radiative forcing and thus potentially to emissions as well. Hence this metric could allow rapid evaluation of the effects of emissions policies at a finer scale than global metrics without requiring use of a full climate model.

  5. Absolute Control in the Canadian Gravity Standardization Net: Challenges and Opportunities

    NASA Astrophysics Data System (ADS)

    Henton, J. A.; Liard, J. O.; Lambert, A.; Pagiatakis, S. D.; Gagnon, C.; Courtier, N.

    2001-12-01

    The Canadian Gravity Standardization Net (CGSN), a network of primary and secondary gravity sites, provides the reference linkage for regional and local gravity surveys performed in different places and at different epochs in Canada. Maintained over the last five decades, CSGN has produced a reliable determination of the gravitational potential as well as associated temporal variations upon the Earth's surface. As part of CGSN more than 50 absolute gravity stations have been established across Canada. This network of absolute gravity sites is designed to provide absolute control for the CGSN and to continue the monitoring of temporal variations resulting from glacial isostatic adjustment, tectonic deformation and other processes. Monitoring of temporal gravity change rates at key, continuous GPS sites is an important step towards maintenance of an integrated reference system. A major benefit from this activity will be a much improved knowledge of temporal variations in the tide gauge reference system required in the monitoring of global sea level change. The primary site for evaluating the stability of the absolute gravimeters for this network is the Canadian Absolute Gravity Site (CAGS), located near Ottawa at Cantley, Quebec (Lat. 45.585° N, Long. 75.807° W). CAGS is the base station for all JILA-2 and A10-003 field measurements as well as housing the Canadian Superconducting Gravimeter Installation (CSGI) which is contributing continuous data to the Global Geodynamics Project (1997-2003). Although owned by a consortium of Canadian universities, superconducting gravimeter GWR12 is operated with the assistance of the Geodetic Survey Division and provides a data stream which can be compared with frequent, repeated absolute gravity measurements. Additional CAGS/CSGI on-site data include: continuous water-level measurements from shallow (10m) and deep (120m) wells, observations from meteorological instrumentation, and continuous Global Positioning System (GPS) observations. Using the data available from CAGS and other sites across Canada, we have begun to carry out a systematic self-consistent and complete synthesis, evaluation and interpretation of all available absolute gravity data over the last decade. Data from superconducting gravimeter GWR12 coupled with available absolute measurements are used to test models of seasonal variations in gravity at the CAGS base station due to groundwater effects identified in earlier work (Bower and Courtier, 1998). These seasonal variations are taken into account when simultaneously solving for the instrumental offset history of JILA-2 and the gravity trends at individual sites. At various field sites across Canada where absolute measurements have been made with different instruments (e.g., FG5-106 (Geological Survey of Canada) and JILA-2 (Geodetic Survey Division)), precise modeling of non-linear, vertical gravity gradients is required to facilitate integration of results. The Western Canada Deformation Array (GPS) reference site at Penticton, British Columbia has been singled out as a key field site where a comparison of the temporal rate of change of gravity with the GPS height rate is highly desirable.

  6. Testing the quasi-absolute method in photon activation analysis

    NASA Astrophysics Data System (ADS)

    Sun, Z. J.; Wells, D.; Starovoitova, V.; Segebade, C.

    2013-04-01

    In photon activation analysis (PAA), relative methods are widely used because of their accuracy and precision. Absolute methods, which are conducted without any assistance from calibration materials, are seldom applied for the difficulty in obtaining photon flux in measurements. This research is an attempt to perform a new absolute approach in PAA - quasi-absolute method - by retrieving photon flux in the sample through Monte Carlo simulation. With simulated photon flux and database of experimental cross sections, it is possible to calculate the concentration of target elements in the sample directly. The QA/QC procedures to solidify the research are discussed in detail. Our results show that the accuracy of the method for certain elements is close to a useful level in practice. Furthermore, the future results from the quasi-absolute method can also serve as a validation technique for experimental data on cross sections. The quasi-absolute method looks promising.

  7. Three-Dimensional Infrared Metamaterial with Asymmetric Transmission

    E-print Network

    Three-Dimensional Infrared Metamaterial with Asymmetric Transmission George Kenanakis,*, Aggelos in the optical region. KEYWORDS: metamaterials, chiral media, split-cube resonators, asymmetric transmission, direct laser writing Electromagnetic metamaterials (MMs) are artificial complex materials composed

  8. Valuation Network Representation and Solution of Asymmetric Decision Problems

    E-print Network

    Shenoy, Prakash P.

    2000-03-16

    This paper deals with asymmetric decision problems. We describe a generalization of the valuation network representation and solution technique to enable efficient representation and solution of asymmetric decision problems. The generalization...

  9. Generating Signals with Multiscale Time Irreversibility: The Asymmetric

    E-print Network

    time series with ``tunable'' multiscale asymmetry to test such indices. We introduce an asymmetric Weierstrass function WA (constructed from asymmetric saw- tooth functions instead of cosine waves) that can

  10. Stochastic Differential Games with Asymmetric Information

    SciTech Connect

    Cardaliaguet, Pierre Rainer, Catherine

    2009-02-15

    We investigate a two-player zero-sum stochastic differential game in which the players have an asymmetric information on the random payoff. We prove that the game has a value and characterize this value in terms of dual viscosity solutions of some second order Hamilton-Jacobi equation.

  11. Attentional Control and Asymmetric Associative Priming

    ERIC Educational Resources Information Center

    Hutchison, Keith A.; Heap, Shelly J.; Neely, James H.; Thomas, Matthew A.

    2014-01-01

    Participants completed a battery of 3 attentional control (AC) tasks (OSPAN, antisaccade, and Stroop, as in Hutchison, 2007) and performed a lexical decision task with symmetrically associated (e.g., "sister-brother") and asymmetrically related primes and targets presented in both the forward (e.g., "atom-bomb") and backward…

  12. Asymmetric hindwing foldings in rove beetles.

    PubMed

    Saito, Kazuya; Yamamoto, Shuhei; Maruyama, Munetoshi; Okabe, Yoji

    2014-11-18

    Foldable wings of insects are the ultimate deployable structures and have attracted the interest of aerospace engineering scientists as well as entomologists. Rove beetles are known to fold their wings in the most sophisticated ways that have right-left asymmetric patterns. However, the specific folding process and the reason for this asymmetry remain unclear. This study reveals how these asymmetric patterns emerge as a result of the folding process of rove beetles. A high-speed camera was used to reveal the details of the wing-folding movement. The results show that these characteristic asymmetrical patterns emerge as a result of simultaneous folding of overlapped wings. The revealed folding mechanisms can achieve not only highly compact wing storage but also immediate deployment. In addition, the right and left crease patterns are interchangeable, and thus each wing internalizes two crease patterns and can be folded in two different ways. This two-way folding gives freedom of choice for the folding direction to a rove beetle. The use of asymmetric patterns and the capability of two-way folding are unique features not found in artificial structures. These features have great potential to extend the design possibilities for all deployable structures, from space structures to articles of daily use. PMID:25368178

  13. Asymmetric hindwing foldings in rove beetles

    PubMed Central

    Saito, Kazuya; Yamamoto, Shuhei; Maruyama, Munetoshi; Okabe, Yoji

    2014-01-01

    Foldable wings of insects are the ultimate deployable structures and have attracted the interest of aerospace engineering scientists as well as entomologists. Rove beetles are known to fold their wings in the most sophisticated ways that have right–left asymmetric patterns. However, the specific folding process and the reason for this asymmetry remain unclear. This study reveals how these asymmetric patterns emerge as a result of the folding process of rove beetles. A high-speed camera was used to reveal the details of the wing-folding movement. The results show that these characteristic asymmetrical patterns emerge as a result of simultaneous folding of overlapped wings. The revealed folding mechanisms can achieve not only highly compact wing storage but also immediate deployment. In addition, the right and left crease patterns are interchangeable, and thus each wing internalizes two crease patterns and can be folded in two different ways. This two-way folding gives freedom of choice for the folding direction to a rove beetle. The use of asymmetric patterns and the capability of two-way folding are unique features not found in artificial structures. These features have great potential to extend the design possibilities for all deployable structures, from space structures to articles of daily use. PMID:25368178

  14. Asymmetric Time Evolution and Indistinguishable Events

    SciTech Connect

    Bryant, P. W.

    2010-11-25

    With a time asymmetric theory, in which quantum mechanical time evolution is given by a semigroup of operators rather than by a group, the states of open systems are represented by density operators exhibiting a branching behavior. To treat the indistinguishably of the members of experimental ensembles, we hypothesize that environmental interference occurs during events that are themselves fundamentally indistinguishable.

  15. Asymmetric -tube Support Vector Regression Xiaolin Huanga,

    E-print Network

    Regression (-SVR) has become a standard tool in nonparametric regression tasks. The -SVRs extend standardAsymmetric -tube Support Vector Regression Xiaolin Huanga, , Lei Shia,c , Kristiaan Pelckmansb-known -tube Support Vector Regression (-SVR) is an effective method for implementing this idea in the context

  16. Dynamic Spectrum Negotiation with Asymmetric Information

    E-print Network

    Huang, Jianwei

    Dynamic Spectrum Negotiation with Asymmetric Information Yang Yan , Jianwei Huang , Xiaofeng Zhong.tsinghua.edu.cn,jwhuang@ie.cuhk.edu.hk,{zhongxf, wangj}@tsinghua.edu.cn Abstract. Spectrum scarcity is becoming a serious issue due to the rapid the spectrum usage by allowing secondary unlicensed users (SUs) to dynamically and opportunistically share

  17. Mach bands change asymmetrically during solar eclipses.

    PubMed

    Ross, John; Diamond, Mark R; Badcock, David R

    2003-01-01

    Observations made during two partial eclipses of the Sun show that the Mach bands on shadows cast by the Sun disappear and reappear asymmetrically as an eclipse progresses. These changes can be explained as due to changes in the shape of the penumbras of shadows as the visible portion of the Sun forms crescents of different orientation. PMID:12892435

  18. Charge asymmetric cosmic rays as a probe of flavor violating asymmetric dark matter

    SciTech Connect

    Masina, Isabella; Sannino, Francesco E-mail: sannino@cp3-origins.net

    2011-09-01

    The recently introduced cosmic sum rules combine the data from PAMELA and Fermi-LAT cosmic ray experiments in a way that permits to neatly investigate whether the experimentally observed lepton excesses violate charge symmetry. One can in a simple way determine universal properties of the unknown component of the cosmic rays. Here we attribute a potential charge asymmetry to the dark sector. In particular we provide models of asymmetric dark matter able to produce charge asymmetric cosmic rays. We consider spin zero, spin one and spin one-half decaying dark matter candidates. We show that lepton flavor violation and asymmetric dark matter are both required to have a charge asymmetry in the cosmic ray lepton excesses. Therefore, an experimental evidence of charge asymmetry in the cosmic ray lepton excesses implies that dark matter is asymmetric.

  19. Asymmetric Bulkheads for Cylindrical Pressure Vessels

    NASA Technical Reports Server (NTRS)

    Ford, Donald B.

    2007-01-01

    Asymmetric bulkheads are proposed for the ends of vertically oriented cylindrical pressure vessels. These bulkheads, which would feature both convex and concave contours, would offer advantages over purely convex, purely concave, and flat bulkheads (see figure). Intended originally to be applied to large tanks that hold propellant liquids for launching spacecraft, the asymmetric-bulkhead concept may also be attractive for terrestrial pressure vessels for which there are requirements to maximize volumetric and mass efficiencies. A description of the relative advantages and disadvantages of prior symmetric bulkhead configurations is prerequisite to understanding the advantages of the proposed asymmetric configuration: In order to obtain adequate strength, flat bulkheads must be made thicker, relative to concave and convex bulkheads; the difference in thickness is such that, other things being equal, pressure vessels with flat bulkheads must be made heavier than ones with concave or convex bulkheads. Convex bulkhead designs increase overall tank lengths, thereby necessitating additional supporting structure for keeping tanks vertical. Concave bulkhead configurations increase tank lengths and detract from volumetric efficiency, even though they do not necessitate additional supporting structure. The shape of a bulkhead affects the proportion of residual fluid in a tank that is, the portion of fluid that unavoidably remains in the tank during outflow and hence cannot be used. In this regard, a flat bulkhead is disadvantageous in two respects: (1) It lacks a single low point for optimum placement of an outlet and (2) a vortex that forms at the outlet during outflow prevents a relatively large amount of fluid from leaving the tank. A concave bulkhead also lacks a single low point for optimum placement of an outlet. Like purely concave and purely convex bulkhead configurations, the proposed asymmetric bulkhead configurations would be more mass-efficient than is the flat bulkhead configuration. In comparison with both purely convex and purely concave configurations, the proposed asymmetric configurations would offer greater volumetric efficiency. Relative to a purely convex bulkhead configuration, the corresponding asymmetric configuration would result in a shorter tank, thus demanding less supporting structure. An asymmetric configuration provides a low point for optimum location of a drain, and the convex shape at the drain location minimizes the amount of residual fluid.

  20. Leveraging the Asymmetric Sensitivity of Eye Contact for Videoconferencing

    E-print Network

    Stanford University

    Leveraging the Asymmetric Sensitivity of Eye Contact for Videoconferencing Milton Chen Computer that the sensitivity to eye contact is asymmetric, in that we are an order of magnitude less sensitive to eye contact and present our discovery that the sensitivity to eye contact is asymmetric. We are an order of magnitude less

  1. Tremorgenic indole alkaloids. The total synthesis of (-)-penitrem D.

    PubMed

    Smith, Amos B; Kanoh, Naoki; Ishiyama, Haruaki; Minakawa, Noriaki; Rainier, Jon D; Hartz, Richard A; Cho, Young Shin; Cui, Haifeng; Moser, William H

    2003-07-01

    A convergent, stereocontrolled total synthesis of the architecturally complex tremorgenic indole alkaloid (-)-penitrem D (4) has been achieved. Highlights of the synthesis include an efficient, asymmetric synthesis of the western hemisphere; the stereocontrolled assembly of the I-ring; discovery of a novel autoxidation to introduce the C(22) tertiary hydroxyl group, required for tremorgenic activity; union of fully elaborated eastern and western hemispheres, exploiting an indole synthetic protocol developed expressly for this purpose; and a late-stage, stereoselective construction of the A and F rings exploiting a Sc(OTf)(3-)promoted reaction cascade. The longest linear sequence leading to (-)-penitrem D (4) was 43 steps. PMID:12837093

  2. Measuring health disparities: a comparison of absolute and relative disparities

    PubMed Central

    Beckles, Gloria L.A.

    2015-01-01

    Monitoring national trends in disparities in different diseases could provide measures to evaluate the impact of intervention programs designed to reduce health disparities. In the US, most of the reports that track health disparities provided either relative or absolute disparities or both. However, these two measures of disparities are not only different in scale and magnitude but also the temporal changes in the magnitudes of these measures can occur in opposite directions. The trends for absolute disparity and relative disparity could move in opposite directions when the prevalence of disease in the two populations being compared either increase or decline simultaneously. If the absolute disparity increases but relative disparity declines for consecutive time periods, the absolute disparity increases but relative disparity declines for the combined time periods even with a larger increase in absolute disparity during the combined time periods. Based on random increases or decreases in prevalence of disease for two population groups, there is a higher chance the trends of these two measures could move in opposite directions when the prevalence of disease for the more advantaged group is very small relative to the prevalence of disease for the more disadvantaged group. When prevalence of disease increase or decrease simultaneously for two populations, the increase or decrease in absolute disparity has to be sufficiently large enough to warrant a corresponding increase or decrease in relative disparity. When absolute disparity declines but relative disparity increases, there is some progress in reducing disparities, but the reduction in absolute disparity is not large enough to also reduce relative disparity. When evaluating interventions to reduce health disparities using these two measures, it is important to consider both absolute and relative disparities and consider all the scenarios discussed in this paper to assess the progress towards reducing or eliminating health disparities. PMID:26623191

  3. Asymmetric dimethylarginine, a biomarker of cardiovascular complications in diabetes mellitus

    PubMed Central

    Konya, Hiroyuki; Miuchi, Masayuki; Satani, Kahori; Matsutani, Satoshi; Yano, Yuzo; Tsunoda, Taku; Ikawa, Takashi; Matsuo, Toshihiro; Ochi, Fumihiro; Kusunoki, Yoshiki; Tokuda, Masaru; Katsuno, Tomoyuki; Hamaguchi, Tomoya; Miyagawa, Jun-ichiro; Namba, Mitsuyoshi

    2015-01-01

    Cardiovascular (CV) complications are an essential causal element of prospect in diabetes mellitus (DM), with carotid atherosclerosis being a common risk factor for prospective crisis of coronary artery diseases and/or cerebral infarction in DM subjects. From another point of view, asymmetric dimethylarginine (ADMA) has been established as an inhibitor of endogenous nitric oxide synthesis and the relationship between ADMA and arteriosclerosis has been reported. In our study with 87 type 2 DM (T2DM) patients, we have examined whether ADMA and other CV risk factors are the useful predictors of DMCV complications. After the measurement of the respective CV risk factors, we have followed the enrolled T2DM patients for 5 years. We have finally analyzed 77 patients. DMCV complications developed in 15 cases newly within 5 years, and 4 cases recurred. The concentrations of ADMA in plasma were markedly more elevated in 19 DM patients with CV complications than in 58 DM patients without CV complications. Urinary albumin (U-Alb), mean intimal-medial thickness (IMT) and ankle brachial index (ABI) were also higher in patients with CV complications. Multiple regression analyses showed that U-Alb had an influence on the high level of ADMA (standardized ? = 6.59, P = 0.00014) independently of age, systolic BP, fibrinogen, mean IMT, plaque score, and ABI. The review indicates what is presently known regarding plasma ADMA that might be a new and meaningful biomarker of CV complications in DM subjects. PMID:25992325

  4. Asymmetric dimethylarginine as a mediator of vascular dysfunction in cirrhosis

    PubMed Central

    Lluch, Paloma; Segarra, Gloria; Medina, Pascual

    2015-01-01

    Cirrhosis is associated with marked abnormalities in the circulatory function that involve a reduction in systemic vascular resistance. An important cause of this vasodilatation is the increased production or activity of nitric oxide (NO) in the splanchnic circulation. During portal hypertension and cirrhosis an increased endothelial NO synthase (eNOS) activity is demonstrated in splanchnic vessels. In contrast, the activity of eNOS in the cirrhotic liver is decreased, which suggests a different regulation of eNOS in the liver and in the splanchnic vessels. Asymmetric dimethylarginine (ADMA) is an endogenous NO inhibitor and higher plasma levels of ADMA are related to increased cardiovascular risk in both the general population and among patients with cirrhosis. It has been demonstrated that the liver is a key player in the metabolism of ADMA. This observation was further supported by investigations in human patients, showing a close correlation between ADMA plasma levels and the degree of hepatic dysfunction. ADMA is degraded to citrulline and dimethylamine by dimethylarginine dimethylaminohydrolases (DDAHs). DDAHs are expressed as type 1 and 2 isoforms and are widely distributed in various organs and tissues, including the liver. In this review, we discuss experimental and clinical data that document the effects of dimethylarginines on vascular function in cirrhosis. Our increasing understanding of the routes of synthesis and metabolism of methylarginines is beginning to provide insights into novel mechanisms of liver disease and allowing us to identify potential therapeutic opportunities. PMID:26327755

  5. Asymmetric Dimethylarginine (ADMA): a promising biomarker for cardiovascular disease?

    PubMed

    Bouras, Georgios; Deftereos, Spyridon; Tousoulis, Dimitrios; Giannopoulos, Georgios; Chatzis, Georgios; Tsounis, Dimitrios; Cleman, Michael W; Stefanadis, Christodoulos

    2013-01-01

    Asymmetric Dimethylarginine (ADMA) is an endogenous inhibitor of nitric oxide (NO) production. ADMA is generated from methylation of arginine residues by protein arginine methyltransferases (PRMTs) and subsequent proteolysis, while its elimination is achieved mainly by degradation with dimethylarginine dimethylaminohydrolase (DDAH). Oxidative stress, endothelial nitric oxide synthase (eNOS) inhibition, eNOS uncoupling, inflammation and shear stress play a pivotal role in ADMA pathophysiology by managing PRMT/DDAH expression and NO synthesis and leading to a common result - endothelial dysfunction. Endothelial dysfunction seems to be the common finding in studies investigating the role of ADMA in cardiovascular disease (CVD). High-performance liquid chromatography (HPLC), mass spectrometry (MS) and enzyme-linked immunosorbent assay (ELISA) are the existing methods for ADMA quantification. However, none of them fulfils all the criteria to be characterized as "gold standard". ADMA is significantly associated with risk factors for CVD and almost with every disease of the cardiovascular system; showing an independent, strong prognostic value for mortality and future cardiovascular events. This article aims to review the current knowledge about ADMA biology and metabolism, pathophysiological mechanisms implicating ADMA in CVD, methods for the determination of ADMA and its association with CVD risk factors and established CVDs. PMID:23470077

  6. Endogenous Asymmetric Dimethylarginine Pathway in High Altitude Adapted Yaks

    PubMed Central

    Mizuno, Shiro; Ishizaki, Takeshi; Toga, Hirohisa; Sakai, Akio; Isakova, Jainagul; Taalaibekova, Elnura; Baiserkeev, Zamirbek; Kojonazarov, Baktybek; Aldashev, Almaz

    2015-01-01

    Hypoxia-induced and high altitude pulmonary hypertension are a major problem in the mountain areas of the world. The asymmetric methylarginines (ADMA) inhibit nitric oxide (NO) synthesis by competing with L-arginine, and high levels of plasma ADMA predict adverse outcomes in pulmonary hypertension. However, little is known about the regulation of the ADMA-NO pathway in animals adapted to high altitudes. We measured the plasma ADMA concentration, endothelial NO synthase (eNOS), dimethylarginine dimethylaminohydrolases (DDAH) protein expression, and DDAH activities in the lungs from yaks. Although the yaks are hypoxemic, cardiac function and pulmonary arterial pressures are almost normal, and we found decreased DDAH expression and activity in association with reduced plasma ADMA concentrations. The eNOS expression was significantly higher in yaks. These results indicate that augmented endogenous NO activity in yaks through the ADMA-DDAH pathway and eNOS upregulation account for the low pulmonary vascular tone observed in high altitude adapted yaks. PMID:26380264

  7. ABSOLUTE PROPERTIES OF THE ECCENTRIC ECLIPSING BINARY STAR FT ORIONIS

    SciTech Connect

    Sabby, Jeffrey A.; Lacy, Claud H. Sandberg; Ibanoglu, Cafer; Claret, Antonio E-mail: clacy@uark.edu E-mail: claret@iaa.es

    2011-06-15

    Accurate absolute properties are determined for the first time for the 3.15 day period eccentric eclipsing binary star FT Ori based on new absolute photometry, five differential light curves, and a radial velocity curve. The stars appear to be normal for their spectral types, A0 + A2. The orbit is highly eccentric (e = 0.409) and shows apsidal motion with a period of 536 years. The absolute properties and the degree of central mass concentration of the stars are consistent with current theoretical models at an age of 190 Myr.

  8. An All Fiber White Light Interferometric Absolute Temperature Measurement System

    PubMed Central

    Kim, Jeonggon Harrison

    2008-01-01

    Recently the author of this article proposed a new signal processing algorithm for an all fiber white light interferometer. In this article, an all fiber white light interferometric absolute temperature measurement system is presented using the previously proposed signal processing algorithm. Stability and absolute temperature measurement were demonstrated. These two tests demonstrated the feasibility of absolute temperature measurement with an accuracy of 0.015 fringe and 0.0005 fringe, respectively. A hysteresis test from 373K to 873K was also presented. Finally, robustness of the sensor system towards laser diode temperature drift, AFMZI temperature drift and PZT non-linearity was demonstrated.

  9. Absolute instability of a liquid jet in a coflowing stream.

    PubMed

    Utada, Andrew S; Fernandez-Nieves, Alberto; Gordillo, Jose M; Weitz, David A

    2008-01-11

    Cylindrical liquid jets are inherently unstable and eventually break into drops due to the Rayleigh-Plateau instability, characterized by the growth of disturbances that are either convective or absolute in nature. Convective instabilities grow in amplitude as they are swept along by the flow, while absolute instabilities are disturbances that grow at a fixed spatial location. Liquid jets are nearly always convectively unstable. Here we show that two-phase jets can breakup due to an absolute instability that depends on the capillary number of the outer liquid, provided the Weber number of the inner liquid is >O(1). We verify our experimental observations with a linear stability analysis. PMID:18232775

  10. Spontaneously self-assembled polar asymmetric multilayers formed by complementary H-bonds

    SciTech Connect

    Johal, M.S.; Smilowitz, L.B.; Robinson, J.M.; McBranch, D.; Li, D.Q.; Cao, Y.W.; Chai, X.D.; Li, T.J.

    1999-08-01

    Ordered molecular assemblies can lead to materials with extremely high second-order nonlinear optical (NLO) properties. Although organic molecules with high nonlinearities are well-known, it has been difficult o design bulk materials in which such molecules are well-aligned. Generating ordered assemblies by the Langmuir-Blodgett (LB) technique often leads to metastable films and is only possible for a narrow range of molecular species while chemical synthesis of covalently bound supramolecular structures on surfaces can be difficult and time-consuming. The formation of polar multilayers by dro-casting is an attractive alternative, especially if such structures lead to thermodynamically stable asymmetric (head-to-tail) assemblies. Asymmetric assemblies are more desirable because the inherent nonlinear optical properties of the molecular layers are additive, whereas in symmetric systems, the nonlinear response cancels within each symmetric bilayer due to destructive interference. In this work, the authors describe the preparation of a novel asymmetric assembly and use sum-frequency generation ({omega}{sub 1} + {omega}{sub 2}) and second-harmonic generation (where {omega}{sub 1} = {omega}{sub 2}) to determine the degree of structural order and the second-order nonlinear susceptibility (d{sub 33}), respectively.

  11. Temporal Dynamics of Microbial Rhodopsin Fluorescence Reports Absolute Membrane Voltage

    PubMed Central

    Hou, Jennifer H.; Venkatachalam, Veena; Cohen, Adam E.

    2014-01-01

    Plasma membrane voltage is a fundamentally important property of a living cell; its value is tightly coupled to membrane transport, the dynamics of transmembrane proteins, and to intercellular communication. Accurate measurement of the membrane voltage could elucidate subtle changes in cellular physiology, but existing genetically encoded fluorescent voltage reporters are better at reporting relative changes than absolute numbers. We developed an Archaerhodopsin-based fluorescent voltage sensor whose time-domain response to a stepwise change in illumination encodes the absolute membrane voltage. We validated this sensor in human embryonic kidney cells. Measurements were robust to variation in imaging parameters and in gene expression levels, and reported voltage with an absolute accuracy of 10 mV. With further improvements in membrane trafficking and signal amplitude, time-domain encoding of absolute voltage could be applied to investigate many important and previously intractable bioelectric phenomena. PMID:24507604

  12. Asteroid Absolute Magnitudes and Geometric Slbedos from Lowell Observatory Database

    NASA Astrophysics Data System (ADS)

    Bowell, E.; Oszkiewicz, D. A.; Wasserman, L. H.; Muinonen, K.; Penttilä, A.; Trilling, D.; Thomas, C.; Pieniluoma, T.

    2012-05-01

    We fit phase functions to photometric data for about half a million asteroids contained in the Lowell Observatory database. We obtain absolute magnitudes for large number of asteroids and geometric albedos for selected objects.

  13. Reliable absolute palaeointensities independent of magnetic domain state

    E-print Network

    Utrecht, Universiteit

    to 5% for artificial samples and natural rocks containing multidomain magnetic particles that wereReliable absolute palaeointensities independent of magnetic domain state Mark J. Dekkers a time. This provides essential constraints for numerical geodynamo models. To date, most palaeointensity

  14. Absolute Value Boundedness, Operator Decomposition, and Stochastic Media and Equations

    NASA Technical Reports Server (NTRS)

    Adomian, G.; Miao, C. C.

    1973-01-01

    The research accomplished during this period is reported. Published abstracts and technical reports are listed. Articles presented include: boundedness of absolute values of generalized Fourier coefficients, propagation in stochastic media, and stationary conditions for stochastic differential equations.

  15. ALMOST REDUCIBILITY AND ABSOLUTE CONTINUITY I ARTUR AVILA

    E-print Network

    Avila, Artur

    ALMOST REDUCIBILITY AND ABSOLUTE CONTINUITY I ARTUR AVILA 1. Introduction Here we consider one of a "global theory", and recent breakthroughs in parameter analysis led to a concrete such 1 #12;2 ARTUR AVILA

  16. Absolute quantification of the Kdp subunits of Escherichia coli by multiple reaction monitoring.

    PubMed

    Surmann, Kristin; Laermann, Vera; Zimmann, Petra; Altendorf, Karlheinz; Hammer, Elke

    2014-07-01

    The sensor kinase/response regulator system KdpD/KdpE of Escherichia coli regulates the expression of the kdpFABC operon, encoding the high-affinity KdpFABC potassium (K(+) )-transport complex. Additionally, it has been suggested that the kdpDE operon itself is subjected to autoregulation by its gene products KdpD and KdpE. However, since kdpFABC and kdpDE expression has mainly been studied on the transcriptional level, accurate information on absolute amounts and the stoichiometric subunit composition of KdpFABC and KdpD/KdpE under K(+) -limiting and K(+) -nonlimiting growth conditions are lacking. In this study, we used highly sensitive mass spectrometric methods to quantify the amount of subunits of the Kdp(F)ABC complex and KdpD/KdpE. Data-dependent shotgun MS was used to assess protein coverage and accessible peptides. Absolute amounts of Kdp(F)ABC and KdpD/KdpE were quantified by targeted MRM analysis in the presence of corresponding heavy labeled standard peptides. Baseline synthesis of Kdp(F)ABC and KdpD/KdpE was found to be in the attomolar range under K(+) -nonlimiting conditions. Under K(+) -limitation, synthesis of Kdp(F)ABC (KdpA:KdpB:KdpC ratio of 1:1:1) was amplified more than 100-fold, whereas only a tenfold amplification of KdpD/KdpE (KdpD:KdpE ratio of 1:4) was observed. The results obtained provide a solid basis for follow-up studies on the dynamic regulation of the Kdp system. PMID:24829208

  17. Absolute and Convective Instability of a Liquid Jet in Microgravity

    NASA Technical Reports Server (NTRS)

    Lin, Sung P.; Vihinen, I.; Honohan, A.; Hudman, Michael D.

    1996-01-01

    The transition from convective to absolute instability is observed in the 2.2 second drop tower of the NASA Lewis Research Center. In convective instability the disturbance grows spatially as it is convected downstream. In absolute instability the disturbance propagates both downstream and upstream, and manifests itself as an expanding sphere. The transition Reynolds numbers are determined for two different Weber numbers by use of Glycerin and a Silicone oil. Preliminary comparisons with theory are made.

  18. Absolute/convective instability of planar viscoelastic jets

    NASA Astrophysics Data System (ADS)

    Ray, Prasun K.; Zaki, Tamer A.

    2015-01-01

    Spatiotemporal linear stability analysis is used to investigate the onset of local absolute instability in planar viscoelastic jets. The influence of viscoelasticity in dilute polymer solutions is modeled with the FENE-P constitutive equation which requires the specification of a non-dimensional polymer relaxation time (the Weissenberg number, We), the maximum polymer extensibility, L, and the ratio of solvent and solution viscosities, ?. A two-parameter family of velocity profiles is used as the base state with the parameter, S, controlling the amount of co- or counter-flow while N-1 sets the thickness of the jet shear layer. We examine how the variation of these fluid and flow parameters affects the minimum value of S at which the flow becomes locally absolutely unstable. Initially setting the Reynolds number to Re = 500, we find that the first varicose jet-column mode dictates the presence of absolute instability, and increasing the Weissenberg number produces important changes in the nature of the instability. The region of absolute instability shifts towards thin shear layers, and the amount of back-flow needed for absolute instability decreases (i.e., the influence of viscoelasticity is destabilizing). Additionally, when We is sufficiently large and N-1 is sufficiently small, single-stream jets become absolutely unstable. Numerical experiments with approximate equations show that both the polymer and solvent contributions to the stress become destabilizing when the scaled shear rate, ? = /W e dU¯1/dx 2L ( /d U ¯ 1 d x 2 is the base-state velocity gradient), is sufficiently large. These qualitative trends are largely unchanged when the Reynolds number is reduced; however, the relative importance of the destabilizing stresses increases tangibly. Consequently, absolute instability is substantially enhanced, and single-stream jets become absolutely unstable over a sizable portion of the parameter space.

  19. Deformation of an asymmetric thin film

    NASA Astrophysics Data System (ADS)

    Geng, Jun; Selinger, Jonathan V.

    2012-09-01

    Experiments have investigated shape changes of polymer films induced by asymmetric swelling by a chemical vapor. Inspired by recent work on the shaping of elastic sheets by non-Euclidean metrics [Y. Klein, E. Efrati, and E. Sharon, ScienceSCIEAS0036-807510.1126/science.1135994 315, 1116 (2007)], we represent the effect of chemical vapors by a change in the target metric tensor. In this problem, unlike that earlier work, the target metric is asymmetric between the two sides of the film. Changing this metric induces a curvature of the film, which may curve into a partial cylinder or a partial sphere. We calculate the elastic energy for each of these shapes and show that the sphere is favored for films smaller than a critical size, which depends on the film thickness, while the cylinder is favored for larger films.

  20. Deformation of an asymmetric thin film

    E-print Network

    Jun Geng; Jonathan V. Selinger

    2011-11-03

    Experiments have investigated shape changes of polymer films induced by asymmetric swelling by a chemical vapor. Inspired by recent work on the shaping of elastic sheets by non-Euclidean metrics [Y. Klein, E. Efrati, and E. Sharon, Science 315, 1116 (2007)], we represent the effect of chemical vapors by a change in the target metric tensor. In this problem, unlike that earlier work, the target metric is asymmetric between the two sides of the film. Changing this metric induces a curvature of the film, which may be curvature into a partial cylinder or a partial sphere. We calculate the elastic energy for each of these shapes, and show that the sphere is favored for films smaller than a critical size, which depends on the film thickness, while the cylinder is favored for larger films.

  1. Asymmetric twins in rhombohedral boron carbide

    SciTech Connect

    Fujita, Takeshi Guan, Pengfei; Madhav Reddy, K.; Hirata, Akihiko; Guo, Junjie; Chen, Mingwei

    2014-01-13

    Superhard materials consisting of light elements have recently received considerable attention because of their ultrahigh specific strength for a wide range of applications as structural and functional materials. However, the failure mechanisms of these materials subjected to high stresses and dynamic loading remain to be poorly known. We report asymmetric twins in a complex compound, boron carbide (B{sub 4}C), characterized by spherical-aberration-corrected transmission electron microscopy. The atomic structure of boron-rich icosahedra at rhombohedral vertices and cross-linked carbon-rich atomic chains can be clearly visualized, which reveals unusual asymmetric twins with detectable strains along the twin interfaces. This study offers atomic insights into the structure of twins in a complex material and has important implications in understanding the planar defect-related failure of superhard materials under high stresses and shock loading.

  2. On Asymmetric Distributions of Satellite Galaxies

    NASA Astrophysics Data System (ADS)

    Bowden, A.; Evans, N. W.; Belokurov, V.

    2014-10-01

    We demonstrate that the asymmetric distribution of M31 satellites cannot be produced by tides from the Milky Way as such effects are too weak. However, loosely bound associations and groups of satellites can fall into larger halos and give rise to asymmetries. We compute the survival times for such associations. We prove that the survival time is always shortest in Keplerian potentials, and can be ~3 times longer in logarithmic potentials. We provide an analytical formula for the dispersal time in terms of the size and velocity dispersion of the infalling structure. We show that, if an association of ~10 dwarfs fell into the M31 halo, its present aspect would be that of an asymmetric disk of satellites. We also discuss the case of cold substructure in the Andromeda II and Ursa Minor dwarfs.

  3. ON ASYMMETRIC DISTRIBUTIONS OF SATELLITE GALAXIES

    SciTech Connect

    Bowden, A.; Evans, N. W.; Belokurov, V.

    2014-10-01

    We demonstrate that the asymmetric distribution of M31 satellites cannot be produced by tides from the Milky Way as such effects are too weak. However, loosely bound associations and groups of satellites can fall into larger halos and give rise to asymmetries. We compute the survival times for such associations. We prove that the survival time is always shortest in Keplerian potentials, and can be ?3 times longer in logarithmic potentials. We provide an analytical formula for the dispersal time in terms of the size and velocity dispersion of the infalling structure. We show that, if an association of ?10 dwarfs fell into the M31 halo, its present aspect would be that of an asymmetric disk of satellites. We also discuss the case of cold substructure in the Andromeda II and Ursa Minor dwarfs.

  4. ASYMMETRIC DIFFUSION OF MAGNETIC FIELD LINES

    SciTech Connect

    Beresnyak, Andrey

    2013-04-20

    Stochasticity of magnetic field lines is important for particle transport properties. Magnetic field lines separate faster than diffusively in turbulent plasma, which is called superdiffusion. We discovered that this superdiffusion is pronouncedly asymmetric, so that the separation of field lines along the magnetic field direction is different from the separation in the opposite direction. While the symmetry of the flow is broken by the so-called imbalance or cross-helicity, the difference between forward and backward diffusion is not directly due to imbalance, but a non-trivial consequence of both imbalance and non-reversibility of turbulence. The asymmetric diffusion perpendicular to the mean magnetic field entails a variety of new physical phenomena, such as the production of parallel particle streaming in the presence of perpendicular particle gradients. Such streaming and associated instabilities could be significant for particle transport in laboratory, space, and astrophysical plasmas.

  5. Towards an asymmetric organocatalytic ?-cyanation of ?-ketoesters

    PubMed Central

    Chowdhury, Raghunath; Schörgenhumer, Johannes; Novacek, Johanna; Waser, Mario

    2015-01-01

    This communication describes the first proof of concept for an asymmetric ?-cyanation of ?-ketoesters using a hypervalent iodine-based electrophilic cyanide-transfer reagent. A series of different organocatalysts has been investigated and it was found that the use of naturally occurring Cinchona alkaloids allows obtaining the target products in good yields and with moderate enantioselectivities up to er = 76:24 under operationally simple conditions. PMID:25843983

  6. Symmetric and asymmetric hybridization in citrus spp. 

    E-print Network

    Bona, Claudine M.

    2009-05-15

    as chromosome elimination may be induced by the high radiation doses. Formation of donor irradiated colonies is avoided, as irradiation prevents donor parental escapes (Derks et al., 1992; Trick et al., 1994). Asymmetric hybrids containing only part... as chromosome elimination is induced by radiation doses (Liu and Deng, 2002; Trick et al., 1994). Liu and Deng (2002) observed that regeneration of shoots from citrus interspecific hybrids was dose dependent. Trick et al. (1994) using tobacco hybridization...

  7. Bidirectional and Asymmetric Quantum Controlled Teleportation

    NASA Astrophysics Data System (ADS)

    Zhang, Da; Zha, Xin-Wei; Duan, Ya-Jun

    2015-05-01

    We propose a new protocol of bidirectional and asymmetric quantum controlled teleportation, using a maximally seven-qubit entangled state as the quantum channel. That is to say Alice wants to transmit an arbitrary single qubit state (an arbitrary two-qubit state) to Bob and Bob wants to transmit an arbitrary two-qubit state (an arbitrary single state) to Alice via the control of the supervisor Charlie.

  8. Global absolut gravity reference system as replacement of IGSN 71

    NASA Astrophysics Data System (ADS)

    Wilmes, Herbert; Wziontek, Hartmut; Falk, Reinhard

    2015-04-01

    The determination of precise gravity field parameters is of great importance in a period in which earth sciences are achieving the necessary accuracy to monitor and document global change processes. This is the reason why experts from geodesy and metrology joined in a successful cooperation to make absolute gravity observations traceable to SI quantities, to improve the metrological kilogram definition and to monitor mass movements and smallest height changes for geodetic and geophysical applications. The international gravity datum is still defined by the International Gravity Standardization Net adopted in 1971 (IGSN 71). The network is based upon pendulum and spring gravimeter observations taken in the 1950s and 60s supported by the early free fall absolute gravimeters. Its gravity values agreed in every case to better than 0.1 mGal. Today, more than 100 absolute gravimeters are in use worldwide. The series of repeated international comparisons confirms the traceability of absolute gravity measurements to SI quantities and confirm the degree of equivalence of the gravimeters in the order of a few µGal. For applications in geosciences where e.g. gravity changes over time need to be analyzed, the temporal stability of an absolute gravimeter is most important. Therefore, the proposition is made to replace the IGSN 71 by an up-to-date gravity reference system which is based upon repeated absolute gravimeter comparisons and a global network of well controlled gravity reference stations.

  9. Measurement of the Absolute Branching Fraction of D{sup 0}{yields}K{sup -}{pi}{sup +}

    SciTech Connect

    Aubert, B.; Bona, M.; Boutigny, D.; Karyotakis, Y.; Lees, J. P.; Poireau, V.; Prudent, X.; Tisserand, V.; Zghiche, A.; Lopez, L.; Palano, A.; Eigen, G.; Ofte, I.; Stugu, B.; Sun, L.; Abrams, G. S.; Battaglia, M.; Brown, D. N.

    2008-02-08

    We measure the absolute branching fraction for D{sup 0}{yields}K{sup -}{pi}{sup +} using partial reconstruction of B{sup 0}{yields}D*{sup +}Xl{sup -}{nu}{sub l} decays, in which only the charged lepton and the pion from the decay D*{sup +}{yields}D{sup 0}{pi}{sup +} are used. Based on a data sample of 230x10{sup 6} BB pairs collected at the {upsilon}(4S) resonance with the BABAR detector at the PEP-II asymmetric-energy B factory at SLAC, we obtain B(D{sup 0}{yields}K{sup -}{pi}{sup +})=(4.007{+-}0.037{+-}0.072)%, where the first uncertainty is statistical and the second is systematic.

  10. Characterization of the Absolute Crystal Polarity across Twin Boundaries in Gallium Phosphide Using Convergent-Beam Electron Diffraction.

    PubMed

    Cohen; McKernan; Carter

    1999-05-01

    : The measurement of absolute crystal polarity is crucial to understanding the structural properties of many planar defects in compound semiconductors. Grain boundaries, including twin boundaries, in the sphalerite lattice are uniquely characterized by the crystallographic misorientation of individual grains and the direction of the crystal polarity in domains adjoining the grain boundary. To evaluate crystal polarity in gallium phosphide (GaP), asymmetrical interference contrast in convergent-beam electron-diffraction (CBED) patterns was used to ascertain the nature and direction of polar bonds. The direction of the asymmetry in the electron diffraction reflections was correlated with the crystal polarity of a sample with known polarity. The CBED technique was applied to determine the polar orientation of grains adjoining Sigma = 3 coherent and lateral twin boundaries in polycrystalline GaP. PMID:10383990

  11. Identification of long-lived proteins retained in cells undergoing repeated asymmetric divisions

    PubMed Central

    Thayer, Nathaniel H.; Leverich, Christina K.; Fitzgibbon, Matthew P.; Nelson, Zara W.; Henderson, Kiersten A.; Gafken, Philip R.; Hsu, Jessica J.; Gottschling, Daniel E.

    2014-01-01

    Long-lived proteins have been implicated in age-associated decline in metazoa, but they have only been identified in extracellular matrices or postmitotic cells. However, the aging process also occurs in dividing cells undergoing repeated asymmetric divisions. It was not clear whether long-lived proteins exist in asymmetrically dividing cells or whether they are involved in aging. Here we identify long-lived proteins in dividing cells during aging using the budding yeast, Saccharomyces cerevisiae. Yeast mother cells undergo a limited number of asymmetric divisions that define replicative lifespan. We used stable-isotope pulse-chase and total proteome mass-spectrometry to identify proteins that were both long-lived and retained in aging mother cells after ?18 cells divisions. We identified ?135 proteins that we designate as long-lived asymmetrically retained proteins (LARPS). Surprisingly, the majority of LARPs appeared to be stable fragments of their original full-length protein. However, 15% of LARPs were full-length proteins and we confirmed several candidates to be long-lived and retained in mother cells by time-lapse microscopy. Some LARPs localized to the plasma membrane and remained robustly in the mother cell upon cell division. Other full-length LARPs were assembled into large cytoplasmic structures that had a strong bias to remain in mother cells. We identified age-associated changes to LARPs that include an increase in their levels during aging because of their continued synthesis, which is not balanced by turnover. Additionally, several LARPs were posttranslationally modified during aging. We suggest that LARPs contribute to age-associated phenotypes and likely exist in other organisms. PMID:25228775

  12. Asymmetrical loading during non-visual navigation.

    PubMed

    Kolev, Ognyan I; Lafon, Matthieu; Zanelli, Giulia; Berthoz, Alain

    2013-12-17

    Since previous studies showed that loading influences posture and gait, the aim of the present study was to determine the effect of asymmetrical loading on locomotion. The following questions were posed: is there a habituation to asymmetrical loading and what is the effect of immediate unloading? Nine healthy subjects (4 males and 5 females) were tested. They had to memorize visually a triangle drawn on the floor and then to walk clockwise and counterclockwise along it in darkness and blindfolded under the following conditions: baseline, loading of right shoulder with 20% of the body weight, after 30 min of habituation to the weight, and immediately after unloading. The turns in degrees around the angles and the distance of the path in cm were measured. The present study demonstrated that asymmetrical loading, which leads to changes in the somatosensory afferentation, affects the human locomotor pattern. There is a habituation effect as well as an unloading effect. There was also a difference between the changes in clockwise and counterclockwise locomotion. Several hypotheses are discussed to explain the results obtained under all conditions. PMID:24466596

  13. Asymmetrical Loading during Non-Visual Navigation.

    PubMed

    Kolev, Ognyan I; Lafon, Matthieu; Zanelli, Giulia; Berthoz, Alain

    2013-10-25

    Since previous studies showed that loading influences posture and gait, the aim of the present study was to determine the effect of asymmetrical loading on locomotion. The following questions were posed: is there a habituation to asymmetrical loading and what is the effect of immediate unloading? Nine healthy subjects (4 males and 5 females) were tested. They had to memorize visually a triangle drawn on the floor and then to walk clockwise and counterclockwise along it in darkness and blindfolded under the following conditions: baseline, loading of right shoulder with 20% of the body weight, after 30min of habituation to the weight, and immediately after unloading. The turns in degrees around the angles and the distance of the path in cm were measured. The present study demonstrated that asymmetrical loading, which leads to changes in the somatosensory afferentation, affects the human locomotor pattern. There is a habituation effect as well as an unloading effect. There was also a difference between the changes in clockwise and counterclockwise locomotion. Several hypotheses are discussed to explain the results obtained under all conditions. PMID:24513298

  14. Development of the titanium–TADDOLate-catalyzed asymmetric fluorination of ?-ketoesters

    PubMed Central

    Hintermann, Lukas; Perseghini, Mauro

    2011-01-01

    Summary Titanium-based Lewis acids catalyze the ?-fluorination of ?-ketoesters by electrophilic N–F-fluorinating reagents. Asymmetric catalysis with TADDOLato–titanium(IV) dichloride (TADDOL = ?,?,?',?'-tetraaryl-(1,3-dioxolane-4,5-diyl)-dimethanol) Lewis acids produces enantiomerically enriched ?-fluorinated ?-ketoesters in up to 91% enantiomeric excess, with either F–TEDA (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)) in acetonitrile solution or NFSI (N-fluorobenzenesulfonimide) in dichloromethane solution as fluorinating reagents. The effects of various reaction parameters and of the TADDOL ligand structure on the catalytic activity and enantioselectivity were investigated. The absolute configuration of several fluorination products was assigned through correlation. Evidence for ionization of the catalyst complex by chloride dissociation, followed by generation of titanium ?-ketoenolates as key reaction intermediates, was obtained. Based on the experimental findings, a general mechanistic sketch and a steric model of induction are proposed. PMID:22043253

  15. Asymmetric Distribution of Histones during Drosophila Male Germline Stem Cell Asymmetric Divisions

    PubMed Central

    Tran, Vuong; Feng, Lijuan; Chen, Xin

    2014-01-01

    It has long been known that epigenetic changes are inheritable. However, except for DNA methylation, little is known about the molecular mechanisms of epigenetic inheritance. Many types of stem cells undergo asymmetric cell division to generate a self-renewed stem cell and a daughter cell committed for differentiation. Still, whether and how stem cells retain their epigenetic memory remain questions to be elucidated. During the asymmetric division of Drosophila male germline stem cell (GSC), our recent studies revealed that the preexisting histone 3 (H3) are selectively segregated to the GSC, whereas newly synthesized H3 deposited during DNA replication are enriched in the differentiating daughter cell. We propose a two-step model to explain this asymmetric histone distribution. First, prior to mitosis, preexisting histones and newly synthesized histones are differentially distributed at two sets of sister chromatids. Next, during mitosis, the set of sister chromatids that mainly consist of preexisting histones are segregated to GSCs, while the other set of sister chromatids enriched with newly synthesized histones are partitioned to the daughter cell committed for differentiation. In this review, we apply current knowledge about epigenetic inheritance and asymmetric cell division to inform our discussion of potential molecular mechanisms and the cellular basis underlying this asymmetric histone distribution pattern. We will also discuss whether this phenomenon contributes to the maintenance of stem cell identity and resetting chromatin structure in the other daughter cell for differentiation. PMID:23681658

  16. Development of a multi-enzymatic cascade reaction for the synthesis of trans-3-hydroxy-L-proline from L-arginine.

    PubMed

    Hara, Ryotaro; Kitatsuji, Saki; Yamagata, Kai; Kino, Kuniki

    2016-01-01

    Naturally occurring L-hydroxyproline in its four regio- and stereoisomeric forms has been explored as a possible precursor for pharmaceutical agents, yet the selective synthesis of trans-3-hydroxy-L-proline has not been achieved. Our aim was to develop a novel biocatalytic asymmetric method for the synthesis of trans-3-hydroxy-L-proline. So far, we focused on the rhizobial arginine catabolic pathway: arginase and ornithine cyclodeaminase are involved in L-arginine degradation to L-proline via L-ornithine. We hypothesized that trans-3-hydroxy-L-proline should be synthesized if arginase and ornithine cyclodeaminase act on (2S,3S)-3-hydroxyarginine and (2S,3S)-3-hydroxyornithine, respectively. To test this hypothesis, we cloned the genes of L-arginine 3-hydroxylase, arginase, and ornithine cyclodeaminase and overexpressed them in Escherichia coli, with subsequent enzyme purification. After characterization and optimization of each enzyme, a three-step procedure involving L-arginine 3-hydroxylase, arginase, and ornithine cyclodeaminase (in this order) was performed using L-arginine as a starting substrate. At the second step of the procedure, putative hydroxyornithine was formed quantitatively by arginase from (2S,3S)-3-hydroxyarginine. Nuclear magnetic resonance and chiral high-performance liquid chromatography analyses revealed that the absolute configuration of this compound was (2S,3S)-3-hydroxyornithine. In the last step of the procedure, trans-3-hydroxy-L-proline was synthesized selectively by ornithine cyclodeaminase from (2S,3S)-3-hydroxyornithine. Thus, we successfully developed a novel synthetic route, comprised of three reactions, to convert L-arginine to trans-3-hydroxy-L-proline. The excellent selectivity makes this procedure simpler and more efficient than conventional chemical synthesis. PMID:26411456

  17. Polarized endosome dynamics by spindle asymmetry during asymmetric cell division.

    PubMed

    Derivery, Emmanuel; Seum, Carole; Daeden, Alicia; Loubéry, Sylvain; Holtzer, Laurent; Jülicher, Frank; Gonzalez-Gaitan, Marcos

    2015-12-10

    During asymmetric division, fate determinants at the cell cortex segregate unequally into the two daughter cells. It has recently been shown that Sara (Smad anchor for receptor activation) signalling endosomes in the cytoplasm also segregate asymmetrically during asymmetric division. Biased dispatch of Sara endosomes mediates asymmetric Notch/Delta signalling during the asymmetric division of sensory organ precursors in Drosophila. In flies, this has been generalized to stem cells in the gut and the central nervous system, and, in zebrafish, to neural precursors of the spinal cord. However, the mechanism of asymmetric endosome segregation is not understood. Here we show that the plus-end kinesin motor Klp98A targets Sara endosomes to the central spindle, where they move bidirectionally on an antiparallel array of microtubules. The microtubule depolymerizing kinesin Klp10A and its antagonist Patronin generate central spindle asymmetry. This asymmetric spindle, in turn, polarizes endosome motility, ultimately causing asymmetric endosome dispatch into one daughter cell. We demonstrate this mechanism by inverting the polarity of the central spindle by polar targeting of Patronin using nanobodies (single-domain antibodies). This spindle inversion targets the endosomes to the wrong cell. Our data uncover the molecular and physical mechanism by which organelles localized away from the cellular cortex can be dispatched asymmetrically during asymmetric division. PMID:26659188

  18. An efficient synthesis of loline alkaloids

    NASA Astrophysics Data System (ADS)

    Cakmak, Mesut; Mayer, Peter; Trauner, Dirk

    2011-07-01

    Loline (1) is a small alkaloid that, in spite of its simple-looking structure, has posed surprising challenges to synthetic chemists. It has been known for more than a century and has been the subject of extensive biological investigations, but only two total syntheses have been achieved to date. Here, we report an asymmetric total synthesis of loline that, with less then ten steps, is remarkably short. Our synthesis incorporates a Sharpless epoxidation, a Grubbs olefin metathesis and an unprecedented transannular aminobromination, which converts an eight-membered cyclic carbamate into a bromopyrrolizidine. The synthesis is marked by a high degree of chemo- and stereoselectivity and gives access to several members of the loline alkaloid family. It delivers sufficient material to support a programme aimed at studying the complex interactions between plants, fungi, insects and bacteria brokered by loline alkaloids.

  19. Development of Ar-BINMOL-Derived Atropisomeric Ligands with Matched Axial and sp(3) Central Chirality for Catalytic Asymmetric Transformations.

    PubMed

    Xu, Zheng; Xu, Li-Wen

    2015-10-01

    Recently, academic chemists have renewed their interest in the development of 1,1'-binaphthalene-2,2'-diol (BINOL)-derived chiral ligands. Six years ago, a working hypothesis, that the chirality matching of hybrid chirality on a ligand could probably lead to high levels of stereoselective induction, prompted us to use the axial chirality of BINOL derivatives to generate new stereogenic centers within the same molecule with high stereoselectivity, obtaining as a result sterically favorable ligands for applications in asymmetric catalysis. This Personal Account describes our laboratory's efforts toward the development of a novel class of BINOL-derived atropisomers bearing both axial and sp(3) central chirality, the so-called Ar-BINMOLs, for asymmetric synthesis. Furthermore, on the basis of the successful application of Ar-BINMOLs and their derivatives in asymmetric catalysis, the search for highly efficient and enantioselective processes also compelled us to give special attention to the BINOL-derived multifunctional ligands with multiple stereogenic centers for use in catalytic asymmetric reactions. PMID:26400411

  20. The 2?{sub 3} Raman overtone of sulfur hexafluoride: Absolute spectra, pressure effects, and polarizability properties

    SciTech Connect

    Chrysos, M. Rachet, F.; Kremer, D.

    2014-03-28

    Of the six normal vibrations of SF{sub 6}, ?{sub 3} has a key role in the mechanisms of radiative forcing. This vibration, though inactive in Raman, shows up through the transition 2?{sub 3} allowing for a complementary view on the asymmetric stretch of the molecule. Here, we look back into this topic, which has already caught some interest in the past but with some points been left out. We make a systematic incoherent-light-scattering analysis of the overtone with the use of different gas pressures and polarization orientations for the incident beam. Absolute-scale isotropic and anisotropic spectra are reported along with natural and pressure-induced widths and shifts, and other spectral features such as the peaks corresponding to the (experimentally indistinguishable) interfering channels E{sub g} and F{sub 2g} hitherto seen solely as two-photon IR-absorption features. We make the first-ever prediction of the SF{sub 6} polarizability second derivative with respect to the ?{sub 3}-mode coordinate and we develop a heuristic argument to explain why the superposition of the three degenerate stretching motions that are related to the ?{sub 3} mode cannot but generate a polarized Raman band.

  1. A Convergent Synthesis of the Proposed Structure of Antitumor Depsipeptide, Stereocalpin A

    PubMed Central

    Ghosh, Arun K.; Xu, Chun-Xiao

    2011-01-01

    The total synthesis of the proposed structure of anticancer agent, stereocalpin A is described. The synthesis features a diastereoselective synthesis of a 5-hydroxy-2,4-dimethyl-3-oxo-octanoic acid unit with asymmetric anti- and syn-aldol reactions as the key steps. Initial cycloamidation led to complete epimerization at the C-11 stereocenter due to unique steric constraints in the 12-membered depsipeptide ring. A late stage methylation strategy led to the synthesis of the proposed structure of stereocalpin A. PMID:19354233

  2. First total synthesis of (+)-Vedelianin, a potent antiproliferative agent

    PubMed Central

    Topczewski, Joseph J.; Wiemer, David F.

    2011-01-01

    The total synthesis of (+)-vedelianin has been accomplished in 18 steps from vanillin. Preparation of a key intermediate in nonracemic form through a Shi epoxidation has allowed determination of the absolute stereochemistry of the natural product as the (2S, 3R, 4aR, 9aR)-isomer. PMID:22053119

  3. AN EVALUATION OF AUTOMATIC PHONE SEGMENTATION FOR CONCATENATIVE SPEECH SYNTHESIS

    E-print Network

    Duh, Kevin

    AN EVALUATION OF AUTOMATIC PHONE SEGMENTATION FOR CONCATENATIVE SPEECH SYNTHESIS Hisashi Kawai the performance of automatic phone segmentation from two viewpoints: (1) temporal precision and (2) effect on the naturalness of synthetic speech. The absolute error of the phone onset time for the best 90% and worst 10

  4. The Role of Scale Interaction on the Asymmetric Rapid Intensification of Typhoon Vicente (2012)

    NASA Astrophysics Data System (ADS)

    Chen, Xiaomin; Wang, Yuqing

    2015-04-01

    Typhoon Vicente (2012) underwent an extreme rapid intensification (RI) with the maximum sustained 10-m wind speed increased by 65 knots within 15 hours just before making landfall in the northern South China Sea according to the best track data of the Joint Typhoon Warning Center (JTWC). In this study, this extreme RI process was successfully reproduced in a cloud-resolving simulation using the Advanced Weather Research and Forecasting Model (ARW-WRF). The RI of Vicente consisted of two modes: (i) an asymmetric mode (i.e. RI onset), represented by relatively slow intensification associated with a distinct eyewall contraction; (ii) an axisymmetric mode with little eyewall contraction. Special attention is paid to the first RI mode in the following analysis. Results from a system-scale tangential momentum budget during the first RI mode indicate that the spin-up of the vortex-scale circulation around the eyewall is mainly attributed to strong convergence/stretching and vertical advection of absolute angular momentum in convective updraft regions while radial eddy flux is responsible for the spin-up of vortex circulation in the eyewall throughout the troposphere. Similarly, the warming within the eye during the RI onset primarily comes from the contribution of radial eddy flux as shown in the potential temperature budget. The two-dimensional spectral decomposition was used to separate the large-scale monsoon trough (with wavelength L > 1000 km) where Vicente was embedded from the TC vortex circulation. This allows quantifying the scale interaction between the monsoon trough and the TC. The results show that the vortex asymmetric vorticity, generated by the strong downshear convective bursts, is advected radially inward by the asymmetric tangential wind projected from the monsoon flow. This process dominates the role of radial eddy flux in spinning up the vortex-scale circulation within the eye and further benefits the eyewall contraction during the first RI mode.

  5. Absolute irradiance of the Moon for on-orbit calibration

    USGS Publications Warehouse

    Stone, T.C.; Kieffer, H.H.

    2002-01-01

    The recognized need for on-orbit calibration of remote sensing imaging instruments drives the ROLO project effort to characterize the Moon for use as an absolute radiance source. For over 5 years the ground-based ROLO telescopes have acquired spatially-resolved lunar images in 23 VNIR (Moon diameter ???500 pixels) and 9 SWIR (???250 pixels) passbands at phase angles within ??90 degrees. A numerical model for lunar irradiance has been developed which fits hundreds of ROLO images in each band, corrected for atmospheric extinction and calibrated to absolute radiance, then integrated to irradiance. The band-coupled extinction algorithm uses absorption spectra of several gases and aerosols derived from MODTRAN to fit time-dependent component abundances to nightly observations of standard stars. The absolute radiance scale is based upon independent telescopic measurements of the star Vega. The fitting process yields uncertainties in lunar relative irradiance over small ranges of phase angle and the full range of lunar libration well under 0.5%. A larger source of uncertainty enters in the absolute solar spectral irradiance, especially in the SWIR, where solar models disagree by up to 6%. Results of ROLO model direct comparisons to spacecraft observations demonstrate the ability of the technique to track sensor responsivity drifts to sub-percent precision. Intercomparisons among instruments provide key insights into both calibration issues and the absolute scale for lunar irradiance.

  6. Econometrics of the Basu Asymmetric Timeliness Coefficient and Accounting Conservatism

    E-print Network

    BALL, RAY

    A substantial literature investigates conditional conservatism, defined as asymmetric accounting recognition of economic shocks (“news”), and how it depends on various market, political, and institutional variables. Studies ...

  7. Study of Optimum Insulating Design Method of Asymmetrical Structure GCB

    NASA Astrophysics Data System (ADS)

    Tanigaki, Shuichi; Yoshioka, Yoshio

    An asymmetrical structure GCB that employed resister closing method equips an interrupter and a closing resister contact in one shield, and so the shield diameter becomes large. In this study, we investigated the optimum tank diameter and major radius of shield electrode of asymmetrical structure GCB by three-dimensional electric field calculation. We also investigated these optimum structures of symmetrical structure GCB and compared the result with that of the asymmetrical structure GCB. In conclusion, the tank diameter of asymmetrical structure GCB becomes larger than the tank diameter of symmetrical structure GCB by 24%.

  8. Water Permeability of Asymmetric Planar Lipid Bilayers

    PubMed Central

    Krylov, Andrey V.; Pohl, Peter; Zeidel, Mark L.; Hill, Warren G.

    2001-01-01

    To understand how plasma membranes may limit water flux, we have modeled the apical membrane of MDCK type 1 cells. Previous experiments demonstrated that liposomes designed to mimic the inner and outer leaflet of this membrane exhibited 18-fold lower water permeation for outer leaflet lipids than inner leaflet lipids (Hill, W.G., and M.L. Zeidel. 2000. J. Biol. Chem. 275:30176–30185), confirming that the outer leaflet is the primary barrier to permeation. If leaflets in a bilayer resist permeation independently, the following equation estimates single leaflet permeabilities: 1/PAB = 1/PA + 1/PB (Eq. l), where PAB is the permeability of a bilayer composed of leaflets A and B, PA is the permeability of leaflet A, and PB is the permeability of leaflet B. Using for the MDCK leaflet–specific liposomes gives an estimated value for the osmotic water permeability (Pf) of 4.6 × 10?4 cm/s (at 25°C) that correlated well with experimentally measured values in intact cells. We have now constructed both symmetric and asymmetric planar lipid bilayers that model the MDCK apical membrane. Water permeability across these bilayers was monitored in the immediate membrane vicinity using a Na+-sensitive scanning microelectrode and an osmotic gradient induced by addition of urea. The near-membrane concentration distribution of solute was used to calculate the velocity of water flow (Pohl, P., S.M. Saparov, and Y.N. Antonenko. 1997. Biophys. J. 72:1711–1718). At 36°C, Pf was 3.44 ± 0.35 × 10?3 cm/s for symmetrical inner leaflet membranes and 3.40 ± 0.34 × 10?4 cm/s for symmetrical exofacial membranes. From , the estimated permeability of an asymmetric membrane is 6.2 × 10?4 cm/s. Water permeability measured for the asymmetric planar bilayer was 6.7 ± 0.7 × 10?4 cm/s, which is within 10% of the calculated value. Direct experimental measurement of Pf for an asymmetric planar membrane confirms that leaflets in a bilayer offer independent and additive resistances to water permeation and validates the use of . PMID:11585847

  9. Crossflow in two-dimensional asymmetric nozzles

    NASA Technical Reports Server (NTRS)

    Sebacher, D. I.; Lee, L. P.

    1975-01-01

    An experimental investigation of the crossflow effects in three contoured, two-dimensional asymmetric nozzles is described. The data were compared with theoretical predictions of nozzle flow by using an inviscid method of characteristics solution and two-dimensional turbulent boundary-layer calculations. The effect of crossflow as a function of the nozzle maximum expansion angle was studied by use of oil-flow techniques, static wall-pressure measurements, and impact-pressure surveys at the nozzle exit. Reynolds number effects on crossflow were investigated.

  10. New ligands for the asymmetric dihydroxylation

    SciTech Connect

    Becker, H.; King, S.B.; Richardson, P.

    1995-12-31

    The asymmetric dibydroxylation of olefins in the presence of cinchona alkaloid derivatives (the AD reaction) has proven to be a reliable method in organic syntheses. For most olefins, the enantioselectivities using the {open_quotes}standard{close_quotes} phathalazine ligands are excellent; however, facial selectivity is still moderate for some olefins. 2,3-Diphenyl pyrazinopyridazine (DPP) and anthraquinone (AQN) as spacers for the {open_quotes}pseudo enantiomeric{close_quotes} alkaloids dihydroquinidine (DHQD) or dihydroquinine (DHQ) give superior enantioselectivities for almost all olefins.

  11. RHIC operation with asymmetric collisions in 2015

    SciTech Connect

    Liu, C.; Aschenauer, C.; Atoian, G.; Blaskiewicz, M.; Brown, K. A.; Bruno, D.; Connolly, R.; Ottavio, T. D.; Drees, K. A.; Fischer, W.; Gardner, C. J.; Gu, X.; Hayes, T.; Huang, H.; Laster, J. S.; Luo, Y.; Makdisi, Y.; Marr, G.; Marusic, A.; Meot, F.; Mernick, K.; Michnoff, R.; Minty, M.; Montag, C.; Morris, J.; Narayan, G.; Nayak, S.; Nemesure, S.; Pile, P.; Poblaguev, A.; Ranjbar, V.; Robert-Demolaize, G.; Roser, T.; Schmidke, B.; Schoefer, V.; Severino, F.; Shrey, T.; Smith, K.; Steski, D.; Tepikian, S.; Trbojevic, D.; Tsoupas, N.; Wang, G.; White, S.; Yip, K.; Zaltsman, A.; Zeno, K.; Zhang, S. Y.

    2015-08-07

    To study low-x shadowing/saturation physics as well as other nuclear effects [1], [2], proton-gold (p-Au, for 5 weeks) and proton-Aluminum (p-Al, for 2 weeks) collisions were provided for experiments in 2015 at the Relativistic Heavy Ion Collider (RHIC), with polarized proton beam in the Blue ring and Au/Al beam in the Yellow ring. The special features of the asymmetric run in 2015 will be introduced. The operation experience will be reviewed as well in the report.

  12. Immobilized bisdiazaphospholane catalysts for asymmetric hydroformylation.

    PubMed

    Adint, Tyler T; Landis, Clark R

    2014-06-01

    Condensation reactions of enantiopure bis-3,4-diazaphospholanes (BDPs) that are functionalized with carboxylic acids enable covalent attachment to bead and silica supports. Exposure of tethered BDPs to the hydroformylation catalyst precursor, Rh(acac)(CO)2, yields catalysts for immobilized asymmetric hydroformylation (iAHF) of prochiral alkenes. Compared with homogeneous catalysts, catalysts immobilized on Tentagel resins exhibit similarly high regioselectivity and enantioselectivity. When corrected for apparent catalyst loading, the activity of the immobilized catalysts approaches that of the homogeneous analogues. Excellent recyclability with trace levels of rhodium leaching are observed in batch and flow reactor conditions. Silica-bound catalysts exhibit poorer enantioselectivities. PMID:24742285

  13. Unitarity constraints on asymmetric freeze-in

    E-print Network

    Anson Hook

    2011-08-30

    This paper considers unitarity and CPT constraints on asymmetric freeze-in, the use of freeze-in to store baryon number in a dark sector. In this scenario, Sakharov's out of equilibrium condition is satisfied by placing the visible and hidden sectors at different temperatures while a net visible baryon number is produced by storing negative baryon number in a dark sector. It is shown that unitarity and CPT lead to unexpected cancellations. In particular, the transfer of baryon number cancels completely at leading order.

  14. The superiority of asymmetric alkyl methyl carbonates

    SciTech Connect

    Ein-Eli, Y.; McDevitt, S.F.; Laura, R.

    1998-01-01

    The electrochemical behavior of graphite electrodes cycled galvanostatically versus Li metal in electrolyte solutions containing LiPF{sub 6}, LiC(SO{sub 2}CF{sub 3}){sub 3}, and LiN(SO{sub 2}C{sub 2}F{sub 5}){sub 2} in ethyl and methyl alkyl carbonates was studied. The solvents include ethyl methyl, ethyl propyl, methyl propyl, isopropyl methyl, and isopropyl ethyl carbonates. The use of asymmetric, aliphatic alkyl methyl carbonates is shown to be essential to achieve both high capacity and long cycle life with graphite electrodes in Li-ion batteries.

  15. Neuronal alignment on asymmetric textured surfaces

    NASA Astrophysics Data System (ADS)

    Beighley, Ross; Spedden, Elise; Sekeroglu, Koray; Atherton, Timothy; Demirel, Melik C.; Staii, Cristian

    2012-10-01

    Axonal growth and the formation of synaptic connections are key steps in the development of the nervous system. Here, we present experimental and theoretical results on axonal growth and interconnectivity in order to elucidate some of the basic rules that neuronal cells use for functional connections with one another. We demonstrate that a unidirectional nanotextured surface can bias axonal growth. We perform a systematic investigation of neuronal processes on asymmetric surfaces and quantify the role that biomechanical surface cues play in neuronal growth. These results represent an important step towards engineering directed axonal growth for neuro-regeneration studies.

  16. de Sitter and double asymmetric brane worlds

    SciTech Connect

    Guerrero, Rommel; Rodriguez, R. Omar; Torrealba, Rafael

    2005-12-15

    Asymmetric brane worlds with dS expansion and static double kink topology are obtained from a recently proposed method and their properties are analyzed. These domain walls interpolate between two spacetimes with different cosmological constants. In the dynamic case, the vacua correspond to dS and AdS geometry, unlike the static case where they correspond to AdS background. We show that it is possible to confine gravity on such branes. In particular, the double-brane world hosts two different walls, so that the gravity is localized on one of them.

  17. Excluding Light Asymmetric Bosonic Dark Matter

    SciTech Connect

    Kouvaris, Chris; Tinyakov, Peter

    2011-08-26

    We argue that current neutron star observations exclude asymmetric bosonic noninteracting dark matter in the range from 2 keV to 16 GeV, including the 5-15 GeV range favored by DAMA and CoGeNT. If bosonic weakly interacting massive particles (WIMPs) are composite of fermions, the same limits apply provided the compositeness scale is higher than {approx}10{sup 12} GeV (for WIMP mass {approx}1 GeV). In the case of repulsive self-interactions, we exclude the large range of WIMP masses and interaction cross sections which complements the constraints imposed by observations of the Bullet Cluster.

  18. Excluding light asymmetric bosonic dark matter.

    PubMed

    Kouvaris, Chris; Tinyakov, Peter

    2011-08-26

    We argue that current neutron star observations exclude asymmetric bosonic noninteracting dark matter in the range from 2 keV to 16 GeV, including the 5-15 GeV range favored by DAMA and CoGeNT. If bosonic weakly interacting massive particles (WIMPs) are composite of fermions, the same limits apply provided the compositeness scale is higher than ?10¹²??GeV (for WIMP mass ?1??GeV). In the case of repulsive self-interactions, we exclude the large range of WIMP masses and interaction cross sections which complements the constraints imposed by observations of the Bullet Cluster. PMID:21929221

  19. Asymmetric chemical reactions by polarized quantum beams

    NASA Astrophysics Data System (ADS)

    Takahashi, Jun-Ichi; Kobayashi, Kensei

    One of the most attractive hypothesis for the origin of homochirality in terrestrial bio-organic compounds (L-amino acid and D-sugar dominant) is nominated as "Cosmic Scenario"; a chiral impulse from asymmetric excitation sources in space triggered asymmetric reactions on the surfaces of such space materials as meteorites or interstellar dusts prior to the existence of terrestrial life. 1) Effective asymmetric excitation sources in space are proposed as polarized quantum beams, such as circularly polarized light and spin polarized electrons. Circularly polarized light is emitted as synchrotron radiation from tightly captured electrons by intense magnetic field around neutron stars. In this case, either left-or right-handed polarized light can be observed depending on the direction of observation. On the other hand, spin polarized electrons is emitted as beta-ray in beta decay from radioactive nuclei or neutron fireballs in supernova explosion. 2) The spin of beta-ray electrons is longitudinally polarized due to parity non-conservation in the weak interaction. The helicity (the the projection of the spin onto the direction of kinetic momentum) of beta-ray electrons is universally negative (left-handed). For the purpose of verifying the asymmetric structure emergence in bio-organic compounds by polarized quantum beams, we are now carrying out laboratory simulations using circularly polarized light from synchrotron radiation facility or spin polarized electron beam from beta-ray radiation source. 3,4) The target samples are solid film or aqueous solution of racemic amino acids. 1) K.Kobayashi, K.Kaneko, J.Takahashi, Y.Takano, in Astrobiology: from simple molecules to primitive life; Ed. V.Basiuk; American Scientific Publisher: Valencia, 2008. 2) G.A.Gusev, T.Saito, V.A.Tsarev, A.V.Uryson, Origins Life Evol. Biosphere. 37, 259 (2007). 3) J.Takahashi, H.Shinojima, M.Seyama, Y.Ueno, T.Kaneko, K.Kobayashi, H.Mita, M.Adachi, M.Hosaka, M.Katoh, Int. J. Mol. Sci. 10, 3044 (2009). 4) V.I.Burkov, L.A.Goncharova, G.A.Gusev, H.Hashimoto, F.Kaneko, T.Kaneko, K. Kobayashi, H.Mita, E.V.Moiseenko, T.Ogawa, N.G.Poluhina, T.Saito, S.Shima, J.Takahashi, M.Tanaka, Y.Tao, V.A.Tsarev, J.Xu, H.Yabuta, K.Yagi-Watanabe, H.Yan, G.Zhang, Origins Life Evol. Biosphere, 39 295 (2009).

  20. Asymmetric exclusion process with global hopping.

    PubMed

    Arita, Chikashi; Bouttier, Jérémie; Krapivsky, P L; Mallick, Kirone

    2013-10-01

    We study a one-dimensional totally asymmetric simple exclusion process with one special site from which particles fly to any empty site (not just to the neighboring site). The system attains a nontrivial stationary state with a density profile varying over the spatial extent of the system. The density profile undergoes a nonequilibrium phase transition when the average density passes through the critical value 1-[4(1-ln2)](-1)=0.185277..., viz., in addition to the discontinuity in the vicinity of the special site, a shock wave is formed in the bulk of the system when the density exceeds the critical density. PMID:24229129