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Sample records for asymmetric horner-wadsworth-emmons reactions

  1. Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Hansen, E. Louise; Kane, John

    2001-01-01

    A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed by asy...... the allylic stereocenter and the alkene geometry. Thus, a single $gamma@-substituted ester was obtained as the overall product, in high isomeric purity. The method was applied to a synthesis of a subunit of the iejimalides, a group of cytotoxic macrolides.......A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed...... by asymmetric HWE reactions into mixtures of two major $alpha@,$beta@-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution...

  2. Rationalization of Product Selectivities in Asymmetric Horner-Wadsworth-Emmons Reactions by Use of a New Method for Transition-State Modeling

    DEFF Research Database (Denmark)

    Norrby, Per-Ola; Brandt, Peter; Rein, Tobias

    1999-01-01

    A new method for creating a transition-state force field, based on quantum chemical normal-mode analysis, is described. The force field was used to rationalize the experimentally observed product selectivities in asymmetric Horner-Wadsworth-Emmons reactions between some chiral phosphonates and ch...

  3. A Quantum Chemical Exploration of the Horner-Wadsworth-Emmons Reaction

    DEFF Research Database (Denmark)

    Brandt, Peter; Norrby, Per-Ola; Martin, Ivar

    1998-01-01

    The mechanism of the Horner-Wadsworth-Emmons (HWE) reaction has been investigated using high level quantum mechanical calculations on a realistic model system. The solvation contribution has been evaluated using the PCM/DIR method. In the free, anionic system, the rate determining step was found ...

  4. Asymmetric Horner-Wadsworth-Emmons Reactions with meso-Dialdehydes: Scope, Mechanism, and Synthetic Applications

    DEFF Research Database (Denmark)

    Rein, Tobias; Vares, Lauri; Kawasaki, Ikuo

    1999-01-01

    Asymmetric Homer-Wadsworth-Emmons reactions between chiral phosphonate reagents and various meso-dialdehydes have been investigated. A mechanistic model useful for rationalizing the experimentally observed stereoselectivities is presented. Furthermore; strategies for applying these reactions...

  5. Highly selective synthesis of (E)-alkenyl-(pentafluorosulfanyl)benzenes through Horner-Wadsworth-Emmons reaction

    Czech Academy of Sciences Publication Activity Database

    Iakobson, George; Beier, Petr

    2012-01-01

    Roč. 8, 25 Jul (2012), s. 1185-1190 ISSN 1860-5397 R&D Projects: GA ČR GAP207/12/0072 Institutional support: RVO:61388963 Keywords : Horner-Wadsworth-Emmons reaction * pentafluorosulfanyl group * phosphonates * sulfurpentafluoride Subject RIV: CC - Organic Chemistry Impact factor: 2.801, year: 2012

  6. Synthesis of a [(14) C]-steroid intermediate: an application of a nonstabilized Horner-Wadsworth-Emmons olefination approach.

    Science.gov (United States)

    Rivera, Nelo R; Ren, Sumei; Hesk, David

    2015-01-01

    Radiolabeled steroid derivative 1 was successfully prepared using a Horner-Wadsworth-Emmons approach: a [(14) C]-label was efficiently incorporated into the C-18 position of the molecule. Previously published procedures employing other olefination methods are either not applicable due to unavailability of [(14) C]-precursors or suffer from poor reactivity. Copyright © 2015 John Wiley & Sons, Ltd.

  7. Lewis Base Activation of Silyl Acetals: Iridium-Catalyzed Reductive Horner-Wadsworth-Emmons Olefination.

    Science.gov (United States)

    Dakarapu, Udaya Sree; Bokka, Apparao; Asgari, Parham; Trog, Gabriela; Hua, Yuanda; Nguyen, Hiep H; Rahman, Nawal; Jeon, Junha

    2015-12-04

    A Lewis base promoted deprotonative pronucleophile addition to silyl acetals has been developed and applied to the iridium-catalyzed reductive Horner-Wadsworth-Emmons (HWE) olefination of esters and the chemoselective reduction of the resulting enoates. Lewis base activation of silyl acetals generates putative pentacoordinate silicate acetals, which fragment into aldehydes, silanes, and alkoxides in situ. Subsequent deprotonative metalation of phosphonate esters followed by HWE with aldehydes furnishes enoates. This operationally convenient, mechanistically unique protocol converts the traditionally challenging aryl, alkenyl, and alkynyl esters to homologated enoates at room temperature within a single vessel.

  8. Mild one-pot Horner-Wadsworth-Emmons olefination and intramolecular N-arylation for the syntheses of indoles, all regio-isomeric azaindoles, and thienopyrroles.

    Science.gov (United States)

    Choi, Ji Hye; Lim, Hwan Jung

    2015-05-14

    The syntheses of various N-protected aromatic-ring fused pyrrole-2-carboxylate derivatives have been accomplished using mild one-pot Horner-Wadsworth-Emmons olefination and Cu-catalyzed intramolecular N-arylation reactions. The optimized mild one-pot reaction conditions of various 2-bromo arylcarboxaldehydes with commercially available N-protected phosphonoglycine trimethylesters gave the desired aromatic-ring fused pyrrole-2-carboxylates, such as substituted indole-, all regio-isomeric azaindole-, and thienopyrrole-2-carboxylates, in good to excellent yields. These conditions showed broad substrate compatibility, without the loss of the protecting group.

  9. Synthetic Applications of Asymmetric Horner-Wadsworth-Emmons Condensations: Approaches to Marine Natural Products

    DEFF Research Database (Denmark)

    Tullis, Joshua S.; Helquist, Paul; Rein, Tobias

    1999-01-01

    Asymmetric HWE condensations of meso-dialdehyde 1 with chiral phosphonates containing 8-phenylmenthol very directly generate chiral moieties that are seen in a number of cytotoxic natural products. The HWE reactions proceed in good yields with synthetically useful geometric and diastereoselectivi...

  10. A practical and azide-free synthetic approach to oseltamivir from diethyl D-tartrate.

    Science.gov (United States)

    Weng, Jiang; Li, Yong-Bo; Wang, Rui-Bin; Li, Feng-Quan; Liu, Can; Chan, Albert S C; Lu, Gui

    2010-05-07

    A short and practical synthesis of oseltamivir was accomplished in 11 steps from inexpensive and abundant diethyl D-tartrate starting material. This azide-free route featured an asymmetric aza-Henry reaction and a domino nitro-Michael/Horner-Wadsworth-Emmons (HWE) reaction as the key steps to construct the relevant cyclohexene ring of the product, which provided an economical and practical alternative for the synthesis of oseltamivir.

  11. Olefination reactions of phosphorus-stabilized carbon nucleophiles.

    Science.gov (United States)

    Gu, Yonghong; Tian, Shi-Kai

    2012-01-01

    A range of phosphorus-stabilized carbon nucleophiles have been employed for alkene synthesis with high chemo-, regio-, and stereoselectivity. The Wittig, Horner-Wadsworth-Emmons, Horner-Wittig, and Evans-Akiba reactions utilize phosphonium-, phosphonate-, phosphine oxide-, and pentacoordinated phosphorane-stabilized carbanions as nucleophiles, respectively, to undergo olefination with aldehydes or ketones, and each of these transformations has its own advantages and limitations. Modifying the structures of these nucleophiles along with optimizing reaction conditions results in the formation of a wide variety of polysubstituted alkenes in a highly stereoselective manner. The olefination of imines with phosphonium ylides has recently emerged as a useful approach to tune the stereoselectivity for alkene synthesis. This review focuses on recent advances in the stereoselective olefination of phosphorus-stabilized carbon nucleophiles.

  12. "Customizable" units in di- and tripeptides: selective conversion into substituted dehydroamino acids.

    Science.gov (United States)

    Saavedra, Carlos J; Boto, Alicia; Hernández, Rosendo

    2012-07-20

    The selective conversion of serine or threonine units of di- and tripeptides into substituted dehydroamino acids is reported. Thus, these common α-amino acids undergo a scission-phosphorylation process to give α-amino phosphonate residues. A Horner-Wadsworth-Emmons reaction with aldehydes or ketones follows to afford the final products with excellent Z-stereoselectivity (Z:E > 98:2). In this way, a single peptide precursor can selectively be transformed into a variety of derivatives.

  13. Synthesis of the C(18)-C(34) fragment of amphidinolide C and the C(18)-C(29) fragment of amphidinolide F.

    Science.gov (United States)

    Roy, Sudeshna; Spilling, Christopher D

    2010-11-19

    A convergent synthesis of the C(18)-C(34) fragment of amphidinolide C and the C(18)-C(29) fragment of amphidinolide F is reported. The approach involves the synthesis of the common intermediate tetrahydrofuranyl-β-ketophosphonate via cross metathesis, Pd(0)-catalyzed cyclization, and hydroboration-oxidation. The β-ketophosphonate was coupled to three side chain aldehydes using a Horner-Wadsworth-Emmons (HWE) olefination reaction to give dienones, which were reduced with l-selectride to give the fragments of amphidinolide C and F.

  14. Synthesis of the C(18)–C(34) Fragment of Amphidinolide C and the C(18)–C(29) Fragment of Amphidinolide F

    Science.gov (United States)

    Roy, Sudeshna; Spilling, Christopher D.

    2010-01-01

    A convergent synthesis of the C(18)–C(34) fragment of amphidinolide C and the C(18)–C(29) fragment of amphidinolide F is reported. The approach involves the synthesis of the common intermediate tetrahydrofuranyl-β-ketophosphonate via cross metathesis, Pd(0)-catalyzed cyclization and hydroboration-oxidation. The β-ketophosphonate was coupled to three side chain aldehydes using a Horner-Wadsworth-Emmons (HWE) olefination reaction to give dienones, which were reduced with L-selectride to give the fragments of amphidinolide C and F. PMID:21028791

  15. Novel route to 5-position vinyl derivatives of thiolactomycin: Olefination vs. deformylation

    Science.gov (United States)

    Kim, Pilho; Barry, Clifton E.; Dowd*, Cynthia S.

    2006-01-01

    Vinyl and diene derivatives of thiolactomycin have been prepared via Horner-Wadsworth-Emmons olefination from protected 5-formyl-3,5-dimethylthiotetronic acid. Several 4-position protecting groups and a variety of phosphonates were evaluated, with MOM protection and β-ketophosphonates yielding the highest ratio of desired product to deformylated product. PMID:16699591

  16. Synthesis, Structure and Fluorescence Properties of 5,17-Distyryl-25,26,27,28-tetraproproxycalix[4]arenes in the Cone Conformation

    DEFF Research Database (Denmark)

    Larsen, Mogens; Krebs, Frederik C; Jørgensen, Mikkel

    1998-01-01

    The HWE (Horner-Wadsworth-Emmons) reaction performed on the easily obtainable 5,17-diformyl- calix[4]arenes (cone) with arylmethyl phosphorus ylides yielded 5,17-distyryl-25,26,27, 28-tetrapropoxycalix[4]arenes (cone) in high yield and purely in the E/E configuration. Compounds 2-5 were prepared...... this way containing bromine. Subsequent bromine-lithium exchange and reaction with trimethoxyborane yielded the boryl- substituted 5,17-distyrylcalix[4] arenes 6-7a. The structures of 3, 5, and 7a were determined by X-ray diffraction. The photophysical properties of 2 were established by absorption...

  17. Silver-Catalyzed Aldehyde Olefination Using Siloxy Alkynes.

    Science.gov (United States)

    Sun, Jianwei; Keller, Valerie A; Meyer, S Todd; Kozmin, Sergey A

    2010-03-20

    We describe the development of a silver-catalyzed carbonyl olefination employing electron rich siloxy alkynes. This process constitutes an efficient synthesis of trisubstituted unsaturated esters, and represents an alternative to the widely utilized Horner-Wadsworth-Emmons reaction. Excellent diastereoselectivities are observed for a range of aldehydes using either 1-siloxy-1-propyne or 1-siloxy-1-hexyne. This mild catalytic process also enables chemoselective olefination of aldehydes in the presence of either ester or ketone functionality. Furthermore, since no by-products are generated, this catalytic process is perfectly suited for development of sequential reactions that can be carried out in a single flask.

  18. Versatile Stereocontrol in Asymmetric Horner-Wadsworth-Emmons Resolution of a Racemic Diphenylphosphoryl-Protected a-Aminoaldehyde

    DEFF Research Database (Denmark)

    Kreuder, Reinhard; Rein, Tobias; Reiser, Oliver

    1997-01-01

    parameters (geometric selectivities from 66:34 to 98:2, diastereomer ratios between 93:7 and *99:1). The switch in stereoselectivity observed when KHMDS or NaHMDS is used as base instead of KHMDS/18-crown-6 is rationalized as resulting from a change in influence of the aldehyde a-stereocenter from Felkin-Anh-Eisenstein...

  19. Asymmetrically Substituted and π-Conjugated 2,2'-Bipyridine Derivatives: Synthesis, Spectroscopy, Computation, and Crystallography.

    Science.gov (United States)

    Bodapati, Ramakrishna; Sarma, Monima; Kanakati, Arunkumar; Das, Samar K

    2015-12-18

    A new series of monosubstituted styryl- and bistyryl-2,2'-bipyridine luminophores (compounds 16-23) have been synthesized via Horner-Wadsworth-Emmons reaction involving a monophosphonate and donor aromatic aldehydes. In the title chromophores, the amino donors are varied between acyclic and cyclic while the alkoxy donors are varied in terms of their number and position. The absorption maxima of these chromophores shift predominantly due to intramolecular charge transfer (ICT) between different donor and acceptor moieties. The title donor-acceptor molecules exhibit intense fluorescence in solution at room temperature, and their emissive behavior has been found to be highly sensitive to solvent polarity. The fluorescence spectra and quantum yields of all the chromophores were recorded in four different solvent media, and the chromophores 16, 17, 19, and 21 exhibit fluorescence in the solid state too. The influence of the nature and position of the donor functionalities in the conjugated backbone of the bipyridine moiety on the electronic absorption properties of the title chromophores (16-23) has been demonstrated, which has further been corroborated by DFT and TD-DFT computation both in gas phase and in solution phase. The crystal structure of compound 18 has been described as a representative member of the family (16-23).

  20. Metal-Free, Site-Selective Peptide Modification by Conversion of "Customizable" Units into β-Substituted Dehydroamino Acids.

    Science.gov (United States)

    Saavedra, Carlos J; Hernández, Dácil; Boto, Alicia

    2018-01-12

    Our site-selective modification of serine or threonine units in peptides allows the generation of β-substituted dehydroamino acids, which increase peptide resistance to hydrolysis and may improve their biological properties. Both the terminal and internal positions can be modified, and different customizable units can be activated separately. Remarkably, high Z selectivity is achieved, even at internal positions. The conversion involves a one-pot oxidative radical scission/phosphorylation process by using the low-toxicity (diacetoxyiodo)benzene/iodine system as the scission reagent. The resulting α-amino phosphonates undergo a Horner-Wadsworth-Emmons reaction to produce the dehydroamino acid derivatives (in a Z/E ratio of usually >98:2) under mild and metal-free conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Stereocontrolled Synthesis of the C(1)-C(11) Subunit of the Iejimalides

    DEFF Research Database (Denmark)

    Mendlik, Matthew T.; Cottard, Muriel; Rein, Tobias

    1997-01-01

    An enantioselective synthesis of the C(1)-C(11) subunit of the iejimalides has been accomplished through a combination of an asymmetric Homer-Wadsworth-Emmons condensation and a chiral pool approach. (C) 1997 Elsevier Science Ltd....

  2. Synthesis of the ABCDEFG ring system of maitotoxin.

    Science.gov (United States)

    Nicolaou, K C; Aversa, Robert J; Jin, Jian; Rivas, Fatima

    2010-05-19

    Maitotoxin (1) continues to fascinate scientists not only because of its size and potent neurotoxicity but also due to its molecular architecture. To provide further support for its structure and facilitate fragment-based biological studies, we developed an efficient chemical synthesis of the ABCDEFG segment 3 of maitotoxin. (13)C NMR chemical shift comparisons of synthetic 3 with the corresponding values for the same carbons of maitotoxin revealed a close match, providing compelling evidence for the correctness of the originally assigned structure to this polycyclic system of the natural product. The synthetic strategy for the synthesis of 3 relied heavily on our previously developed furan-based technology involving sequential Noyori asymmetric reduction and Achmatowicz rearrangement for the construction of the required tetrahydropyran building blocks, and employed a B-alkyl Suzuki coupling and a Horner-Wadsworth-Emmons olefination to accomplish their assembly and elaboration to the final target molecule.

  3. Dithioacetals as an Entry to Titanium-Alkylidene Chemistry: A New and Efficient Carbonyl Olefination.

    Science.gov (United States)

    Breit, Bernhard

    1998-03-02

    Wittig, Horner-Wadsworth-Emmons, Julia-Lythgoe, Tebbe, Grubbs, and Petasis-when it comes to carbonyl olefinations, these names are familiar to all chemistry students. In the future, the name Takeda will probably have to be added to this list. His recent work on the formation of titanium-alkylidene species from dithioacetals has provided organic chemists with a remarkable method for carbonyl olefination that is generally applicable under neutral to Lewis acidic conditions. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

  4. Total Synthesis of Dolatrienoic Acid: A Subunit of Dolastatin 14.

    Science.gov (United States)

    Mouné, Sylvie; Niel, Gilles; Busquet, Magali; Eggleston, Ian; Jouin, Patrick

    1997-05-16

    The (7R,15R)- and (7S,15R)-diastereomers of dolatrienoic acid were synthesized using a convergent strategy. Fragment C5-C9 was obtained through enantiodifferentiation of racemic pentane-1,3,5-triol as the key step, fixing the chirality at C7 of fragments 4 and ent-4. The chirality at C15 of the fragment C10-C16 was introduced from L-glutamic acid. Coupling of these two fragments led to the aldehydes (7R,15R)- and (7S,15R)-2 which were homologated by Horner-Wadsworth-Emmons condensation to give (7R,15R)- and (7S,15R)-dolatrienoic acids.

  5. Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(-)-myrtenol nitrate.

    Science.gov (United States)

    Bew, Sean P; Hiatt-Gipson, Glyn D; Mills, Graham P; Reeves, Claire E

    2016-01-01

    Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a 'halide for nitrate' substitution. Employing readily available starting materials, reagents and Horner-Wadsworth-Emmons chemistry the synthesis of easily separable, synthetically versatile 'key building blocks' (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, 'off the shelf' materials. Exploiting their reactivity we have studied their ability to undergo an 'allylic halide for allylic nitrate' substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates ('isoprene nitrates') in 66-80% overall yields. Using NOESY experiments the elucidation of the carbon-carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our 'halide for nitrate' substitution chemistry we outline the straightforward transformation of (1R,2S)-(-)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(-)-myrtenol nitrate.

  6. Computer-assisted mechanistic evaluation of organic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gushurst, A.J.

    1988-01-01

    CAMEO, an interactive computer program which predicts the products of organic reactions given starting materials and conditions, has been refined and extended in the area of base-catalyzed and nucleophilic processes. The present capabilities of the program are outlined including brief discussion on the major segments in CAMEO: graphics, perception, and reaction evaluation. The implementation of general algorithms for predicting the acidities of a vast number of organic compounds to within 2 pK{sub a} units in dimethylsulfoxide and water are then described, followed by a presentation of the reactivity rules used by the program to evaluate nucleophilc reactions. Finally, a treatment of sulfur and phosphorus ylides, iminophosphoranes, and P=X-activated anions is given illuminating the various competitions available for these reagents, such as between proton transfer and addition, 1,2- and 1,4-addition, and the Peterson, Wittig, and Horner-Emmons olefination reactions.

  7. Neuroimaging experience in pediatric Horner syndrome

    International Nuclear Information System (INIS)

    Kadom, Nadja; Rosman, N.P.; Jubouri, Shams; Trofimova, Anna; Egloff, Alexia M.; Zein, Wadih M.

    2015-01-01

    Horner syndrome in children is rare. The frequency and spectrum of malignancy as the cause of Horner syndrome in children remains unclear. Also unclear is whether the imaging work-up should include the entire oculo-sympathetic pathway or should be more targeted. In addition, the value of cross-sectional angiographic imaging in Horner syndrome is uncertain. To review imaging pathology in a cohort of children with Horner syndrome at a major academic pediatric medical center. We reviewed a 22-year period of CT and MR imaging studies in children with a clinical diagnosis of Horner syndrome referred for imaging. We found 38 patients who fulfilled study criteria of Horner syndrome and 6/38 had relevant imaging findings: 2/6 etiologies were neoplastic (congenital neuroblastoma and central astrocytoma), 1/6 had a vascular abnormality (hypoplastic carotid artery), 1/6 had maldevelopment (Chiari I malformation), and 2/6 had inflammatory/traumatic etiology (viral cervical lymphadenopathy, post jugular vein cannulation). There was a similar number of congenital and acquired pathologies. The malignancies were found at any level of the oculosympathetic pathway. There are treatable causes, including malignancies, in children presenting with Horner syndrome, which justify imaging work-up of the entire oculosympathetic pathway, unless the lesion level can be determined clinically. (orig.)

  8. Neuroimaging experience in pediatric Horner syndrome

    Energy Technology Data Exchange (ETDEWEB)

    Kadom, Nadja [Boston University School of Medicine, Department of Radiology, Boston University Medical Center, Boston, MA (United States); Rosman, N.P. [Boston Medical Center, Division of Pediatric Neurology, Departments of Pediatrics and Neurology, Boston University School of Medicine, Boston, MA (United States); Jubouri, Shams; Trofimova, Anna; Egloff, Alexia M. [Children' s National Medical Center, Department of Radiology and Diagnostic Imaging, Washington, DC (United States); Zein, Wadih M. [National Eye Institute (NEI), Bethesda, MD (United States)

    2015-09-15

    Horner syndrome in children is rare. The frequency and spectrum of malignancy as the cause of Horner syndrome in children remains unclear. Also unclear is whether the imaging work-up should include the entire oculo-sympathetic pathway or should be more targeted. In addition, the value of cross-sectional angiographic imaging in Horner syndrome is uncertain. To review imaging pathology in a cohort of children with Horner syndrome at a major academic pediatric medical center. We reviewed a 22-year period of CT and MR imaging studies in children with a clinical diagnosis of Horner syndrome referred for imaging. We found 38 patients who fulfilled study criteria of Horner syndrome and 6/38 had relevant imaging findings: 2/6 etiologies were neoplastic (congenital neuroblastoma and central astrocytoma), 1/6 had a vascular abnormality (hypoplastic carotid artery), 1/6 had maldevelopment (Chiari I malformation), and 2/6 had inflammatory/traumatic etiology (viral cervical lymphadenopathy, post jugular vein cannulation). There was a similar number of congenital and acquired pathologies. The malignancies were found at any level of the oculosympathetic pathway. There are treatable causes, including malignancies, in children presenting with Horner syndrome, which justify imaging work-up of the entire oculosympathetic pathway, unless the lesion level can be determined clinically. (orig.)

  9. Horner syndrome: clinical perspectives

    Science.gov (United States)

    Kanagalingam, Sivashakthi; Miller, Neil R

    2015-01-01

    Horner syndrome consists of unilateral ptosis, an ipsilateral miotic but normally reactive pupil, and in some cases, ipsilateral facial anhidrosis, all resulting from damage to the ipsilateral oculosympathetic pathway. Herein, we review the clinical signs and symptoms that can aid in the diagnosis and localization of a Horner syndrome as well as the causes of the condition. We emphasize that pharmacologic testing can confirm its presence and direct further testing and management. PMID:28539793

  10. Advanced astigmatism-corrected tandem Wadsworth mounting for small-scale spectral broadband imaging spectrometer.

    Science.gov (United States)

    Lei, Yu; Lin, Guan-yu

    2013-01-01

    Tandem gratings of double-dispersion mount make it possible to design an imaging spectrometer for the weak light observation with high spatial resolution, high spectral resolution, and high optical transmission efficiency. The traditional tandem Wadsworth mounting is originally designed to match the coaxial telescope and large-scale imaging spectrometer. When it is used to connect the off-axis telescope such as off-axis parabolic mirror, it presents lower imaging quality than to connect the coaxial telescope. It may also introduce interference among the detector and the optical elements as it is applied to the short focal length and small-scale spectrometer in a close volume by satellite. An advanced tandem Wadsworth mounting has been investigated to deal with the situation. The Wadsworth astigmatism-corrected mounting condition for which is expressed as the distance between the second concave grating and the imaging plane is calculated. Then the optimum arrangement for the first plane grating and the second concave grating, which make the anterior Wadsworth condition fulfilling each wavelength, is analyzed by the geometric and first order differential calculation. These two arrangements comprise the advanced Wadsworth mounting condition. The spectral resolution has also been calculated by these conditions. An example designed by the optimum theory proves that the advanced tandem Wadsworth mounting performs excellently in spectral broadband.

  11. Synthesis of a Diamino Substituted Terphenyldivinyl Chromophore

    Directory of Open Access Journals (Sweden)

    Jun-Ru Wang

    2009-06-01

    Full Text Available (E,E-1,4-bis(4'-aminostyryl-2,5-bis(octyloxy-benzene (6 and its derivative (E,E-1,4-bis(4'-acetamidostyryl-2,5-bis(octyloxy-benzene (7 were synthesized and characterized after alkylation, bromomethylation, Horner-Emmons reaction and reduction from hydroquinone. In order to gain more molecular electronic data, HOMO and LUMO of compound 6 have been calculated by Gaussian 03 W.

  12. ORIGINAL ARTICLES Pharmacological testing in Horner's syndrome

    African Journals Online (AJOL)

    topical cocaine 10% in both eyes gave an odds ratio of 1 050:1 that. Horner's syndrome ... nerve endings and therefore do not stimulate the effector cells directly. ... Pharmacological testing in Horner's syndrome – a new paradigm. Derrick P ...

  13. Direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Gnanadesikan, Vijay; Horiuchi, Yoshihiro; Ohshima, Takashi; Shibasaki, Masakatsu

    2004-06-30

    A direct catalytic asymmetric aldol reaction of propionate equivalent was achieved via the aldol-Tishchenko reaction. Coupling an irreversible Tishchenko reaction to a reversible aldol reaction overcame the retro-aldol reaction problem and thereby afforded the products in high enantio and diastereoselectivity using 10 mol % of the asymmetric catalyst. A variety of ketones and aldehydes, including propyl and butyl ketones, were coupled efficiently, yielding the corresponding aldol-Tishchenko products in up to 96% yield and 95% ee. Diastereoselectivity was generally below the detection limit of 1H NMR (>98:2). Preliminary studies performed to clarify the mechanism revealed that the aldol products were racemic with no diastereoselectivity. On the other hand, the Tishchenko products were obtained in a highly enantiocontrolled manner.

  14. First Rib Fracture Resulting in Horner's Syndrome.

    Science.gov (United States)

    Lin, You-Cheng; Chuang, Ming-Tsung; Hsu, Chin-Hao; Tailor, Al-Rahim Abbasali; Lee, Jung-Shun

    2015-12-01

    First rib fractures and traumatic Horner's syndrome are both quite rare, which can make it difficult to properly diagnose the combination of these 2 conditions in the emergency department. These conditions may be associated with severe medical emergencies, such as ongoing carotid dissection. We present the case of a 33-year-old man who sustained fractures to his right second, third, and fourth ribs and a delay in the diagnosis of left Horner's syndrome after he was involved in a traffic accident. Left Horner's syndrome was caused by a left transverse fracture of the first rib. This fracture was not detected on chest radiographs and required a 3-dimensional reconstructed neck computed tomography scan for detection. WHY SHOULD AN EMERGENCY PHYSICIAN BE AWARE OF THIS?: In the diagnosis of carotid artery dissection, conventional angiography is the criterion standard but is considered invasive. CTA is less invasive, time-saving, and can show more anatomic structures in the neck in addition to the carotid arteries. It is a good screening diagnostic modality in the traumatology department. Although the treatments for Horner's syndrome and first rib fracture are conservative, the early diagnosis of both conditions can resolve the anxiety and uncertainty experienced by both doctors and patients. Copyright © 2015 Elsevier Inc. All rights reserved.

  15. Structure-activity relationship studies of 1,7-diheteroarylhepta-1,4,6-trien-3-ones with two different terminal rings in prostate epithelial cell models.

    Science.gov (United States)

    Wang, Rubing; Zhang, Xiaojie; Chen, Chengsheng; Chen, Guanglin; Sarabia, Cristian; Zhang, Qiang; Zheng, Shilong; Wang, Guangdi; Chen, Qiao-Hong

    2017-06-16

    To systematically investigate the structure-activity relationships of 1,7-diheteroarylhepta-1,4,6-trien-3-ones in three human prostate cancer cell models and one human prostate non-neoplastic epithelial cell model, thirty five 1,7-diarylhepta-1,4,6-trien-3-ones with different terminal heteroaromatic rings have been designed for evaluation of their anti-proliferative potency in vitro. These target compounds have been successfully synthesized through two sequential Horner-Wadsworth-Emmons reactions starting from the appropriate aldehydes and tetraethyl (2-oxopropane-1,3-diyl)bis(phosphonate). Their anti-proliferative potency against PC-3, DU-145 and LNCaP human prostate cancer cell lines can be significantly enhanced by the manipulation of the terminal heteroaromatic rings, further demonstrating the utility of 1,7-diarylhepta-1,4,6-trien-3-one as a potential scaffold for the development of anti-prostate cancer agents. The optimal analog 40 is 82-, 67-, and 39-fold more potent than curcumin toward the three prostate cancer cell lines, respectively. The experimental data also reveal that the trienones with two different terminal aromatic rings possess greater potency toward three prostate cancer cell lines, but also have greater capability of suppressing the proliferation of PWR-1E benign human prostate epithelial cells, as compared to the corresponding counterparts with two identical terminal rings and curcumin. The terminal aromatic rings also affect the cell apoptosis perturbation. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  16. Improving multivariate Horner schemes with Monte Carlo tree search

    Science.gov (United States)

    Kuipers, J.; Plaat, A.; Vermaseren, J. A. M.; van den Herik, H. J.

    2013-11-01

    Optimizing the cost of evaluating a polynomial is a classic problem in computer science. For polynomials in one variable, Horner's method provides a scheme for producing a computationally efficient form. For multivariate polynomials it is possible to generalize Horner's method, but this leaves freedom in the order of the variables. Traditionally, greedy schemes like most-occurring variable first are used. This simple textbook algorithm has given remarkably efficient results. Finding better algorithms has proved difficult. In trying to improve upon the greedy scheme we have implemented Monte Carlo tree search, a recent search method from the field of artificial intelligence. This results in better Horner schemes and reduces the cost of evaluating polynomials, sometimes by factors up to two.

  17. An efficient catalyst for asymmetric Reformatsky reaction

    Indian Academy of Sciences (India)

    rate enantioselectivity using N,N-dialkylnorephedrines as chiral ligands. ..... temperatures also, there was no product conversion. ... Optimization of reaction conditions for asymmetric Reformatsky reaction between benzaldehyde and α-.

  18. Síndrome de Claude Bernard-Horner associada ao empiema pleural Claude Bernard-Horner syndrome resulting from pleural empyema

    Directory of Open Access Journals (Sweden)

    Fernando Luiz Westphal

    2006-04-01

    Full Text Available A síndrome de Claude Bernard-Horner apresenta várias etiologias, ocorre por interrupção do estímulo nervoso em qualquer ponto do trajeto do nervo e pode ser intra ou extratorácica. É relatado um caso dessa síndrome causado por empiema pleural septado, localizado em região paravertebral, no terço superior do hemitórax direito. O paciente foi submetido à toracotomia para drenagem da cavidade pleural. A evolução foi satisfatória, com regressão do quadro infeccioso, expansão pulmonar e remissão da síndrome.Claude Bernard-Horner syndrome presents various etiologies and occurs as the direct result of interrupted nerve signaling at any point along the nerve trajectory, be it intrathoracic or extrathoracic. Herein, we report a case of Claude Bernard-Horner syndrome caused by loculated pleural empyema located in the paravertebral region of the upper third of the right hemithorax. The patient was submitted to thoracotomy in order to drain the infected fluids. The end result was satisfactory, including resolution of the infection, pulmonary expansion, and remission of the syndrome.

  19. Responses to Horner and Carr.

    Science.gov (United States)

    Durand, V. Mark; And Others

    1997-01-01

    Five special educators (Durand, Bambara, Dunlap, Kennedy, and Wacker) respond to an article in the same issue by Horner and Carr entitled "Behavioral Support for Students with Severe Disabilities: Functional Assessment and Comprehensive Intervention." Respondents raise concerns regarding the range of intervention options, the behavioral…

  20. Rare Complications of Cervical Spine Surgery: Horner's Syndrome.

    Science.gov (United States)

    Traynelis, Vincent C; Malone, Hani R; Smith, Zachary A; Hsu, Wellington K; Kanter, Adam S; Qureshi, Sheeraz A; Cho, Samuel K; Baird, Evan O; Isaacs, Robert E; Rahman, Ra'Kerry K; Polevaya, Galina; Smith, Justin S; Shaffrey, Christopher; Tortolani, P Justin; Stroh, D Alex; Arnold, Paul M; Fehlings, Michael G; Mroz, Thomas E; Riew, K Daniel

    2017-04-01

    A multicenter retrospective case series. Horner's syndrome is a known complication of anterior cervical spinal surgery, but it is rarely encountered in clinical practice. To better understand the incidence, risks, and neurologic outcomes associated with Horner's syndrome, a multicenter study was performed to review a large collective experience with this rare complication. We conducted a retrospective multicenter case series study involving 21 high-volume surgical centers from the AOSpine North America Clinical Research Network. Medical records for 17 625 patients who received subaxial cervical spine surgery from 2005 to 2011 were reviewed to identify occurrence of 21 predefined treatment complications. Descriptive statistics were provided for baseline patient characteristics. Paired t test was used to analyze changes in clinical outcomes at follow-up compared to preoperative status. In total, 8887 patients who underwent anterior cervical spine surgery at the participating institutions were screened. Postoperative Horner's syndrome was identified in 5 (0.06%) patients. All patients experienced the complication following anterior cervical discectomy and fusion. The sympathetic trunk appeared to be more vulnerable when operating on midcervical levels (C5, C6), and most patients experienced at least a partial recovery without further treatment. This collective experience suggests that Horner's syndrome is an exceedingly rare complication following anterior cervical spine surgery. Injury to the sympathetic trunk may be limited by maintaining a midline surgical trajectory when possible, and performing careful dissection and retraction of the longus colli muscle when lateral exposure is necessary, especially at caudal cervical levels.

  1. Síndrome de Horner após cirurgia estereotáxica para doença de Parkinson Horner syndrome after stereotactic Parkinson's surgery

    Directory of Open Access Journals (Sweden)

    Luiz A. Rogano

    2003-06-01

    Full Text Available Apresentamos estudo de dez pacientes com doença de Parkison, que foram submetidos a procedimentos ablativos estereotáxicos percutâneos e que desenvolveram síndrome de Horner ipsilateral imediatamente após a lesão. Sete pacientes foram submetidos a palidotomia, dois a subtalamotomia (campotomia de Forel e talamotomia e um paciente a subtalamotomia. Sete desenvolveram miose e os dez desenvolveram semiptose ipsilateral à lesão. A ocorrência da síndrome de Horner resulta possivelmente de lesão de fibras simpáticas entre o hipotálamo, campo de Forel e tálamo.We present ten patients with Parkinson's disease who underwent stereotactic ablative radiofrequency procedures. Seven patients underwent pallidotomy, two subthalamotomy and VIM, and one subthalamotomy. Seven developed miosis and all semiptosis ipsilateral immediately after the procedure. The occurrence of Horner's syndrome is probably due to the lesion of sympathetic fibers among hypothalamus, Forel's field and thalamus after the stereotactic procedure.

  2. Imaging of Horner's syndrome

    International Nuclear Information System (INIS)

    George, A.; Haydar, A.A.; Adams, W.M.

    2008-01-01

    Horner's syndrome, or oculosympathetic paresis, results from interruption of the sympathetic trunk innervation to the eye and presents typically with meiosis, ptosis and facial anhydrosis on the affected side. 1 The pathological process ranges from benign, such as cluster headache, or life threatening, such as lung malignancy. Appropriate imaging requires an anatomical appreciation of the complex and circuitous route the neuronal pathway takes as it passes from the central nervous system to the eye

  3. Visual Hallucinations in a Patient with Horner's Syndrome Secondary to Internal Carotid Dissection

    DEFF Research Database (Denmark)

    Singh, Amardeep; Mortzos, Panteleimon; Sørensen, Torben Lykke

    2014-01-01

    A 67-year-old female presented with post-ganglionic Horner's syndrome. In addition to the classical symptoms of Horner's syndrome, the patient reported experiencing frightening complex visual and auditory hallucinations on two different occasions. Magnetic resonance angiography of the cerebrum...

  4. Asymmetric H-D exchange reactions of fluorinated aromatic ketones

    KAUST Repository

    Zhao, Yujun

    2012-01-01

    Chiral bicyclic guanidine catalyzes the asymmetric H-D exchange reactions. Up to 30% ee was achieved. DFT calculations were employed to elucidate and explain the origin of the reaction\\'s stereoselectivity. © 2012 The Royal Society of Chemistry.

  5. Rhabdomyolysis resulting in concurrent Horner's syndrome and brachial plexopathy: a case report

    International Nuclear Information System (INIS)

    Lee, Susan C.; Geannette, Christian; Sneag, Darryl B.; Wolfe, Scott W.; Feinberg, Joseph H.

    2017-01-01

    This case report describes a 29-year-old male who presented with immediate onset of Horner's syndrome and ipsilateral brachial plexopathy after sleeping with his arm dangling outside a car window for 8 h. Outside workup and imaging revealed rhabdomyolysis of the left neck musculature. Subsequent electrodiagnostic testing and high-resolution brachial plexus magnetic resonance imaging at the authors' institution attributed the Horner's syndrome and concurrent brachial plexopathy to rhabdomyolysis of the longus colli and scalene musculature, which had compressed - and consequently scar tethered - the cervical sympathetic trunk and brachial plexus. This case of co-existent Horner's syndrome and brachial plexopathy demonstrates the role of high-resolution brachial plexus MRI in diagnosing plexopathy and the importance of being familiar with plexus and paravertebral muscle anatomy. (orig.)

  6. Rhabdomyolysis resulting in concurrent Horner's syndrome and brachial plexopathy: a case report.

    Science.gov (United States)

    Lee, Susan C; Geannette, Christian; Wolfe, Scott W; Feinberg, Joseph H; Sneag, Darryl B

    2017-08-01

    This case report describes a 29-year-old male who presented with immediate onset of Horner's syndrome and ipsilateral brachial plexopathy after sleeping with his arm dangling outside a car window for 8 h. Outside workup and imaging revealed rhabdomyolysis of the left neck musculature. Subsequent electrodiagnostic testing and high-resolution brachial plexus magnetic resonance imaging at the authors' institution attributed the Horner's syndrome and concurrent brachial plexopathy to rhabdomyolysis of the longus colli and scalene musculature, which had compressed-and consequently scar tethered-the cervical sympathetic trunk and brachial plexus. This case of co-existent Horner's syndrome and brachial plexopathy demonstrates the role of high-resolution brachial plexus MRI in diagnosing plexopathy and the importance of being familiar with plexus and paravertebral muscle anatomy.

  7. Theory and experiment studies of the 1,4-bis(4-methoxylstyryl)benzene as a wavelength shifter of liquid scintillator

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Zhanlong [School of Material Science and Engineering, Southwest University of Science and Technology, Mianyang 621010 (China); Joint Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology and Research Center of Laser Fusion, Mianyang 621010 (China); Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900 (China); Zhu, Jiayi [Joint Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology and Research Center of Laser Fusion, Mianyang 621010 (China); Bi, Yutie, E-mail: biyutie@sina.com [Joint Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology and Research Center of Laser Fusion, Mianyang 621010 (China); Xu, Yewei [School of Material Science and Engineering, Southwest University of Science and Technology, Mianyang 621010 (China); Zhang, Qianfeng [Joint Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology and Research Center of Laser Fusion, Mianyang 621010 (China); Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900 (China); Zhang, Xing [Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900 (China); Li, Junjiang [Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026 (China); Zhang, Lin, E-mail: zhlmy@sina.com [School of Material Science and Engineering, Southwest University of Science and Technology, Mianyang 621010 (China); Joint Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology and Research Center of Laser Fusion, Mianyang 621010 (China); Research Center of Laser Fusion, China Academy of Engineering Physics, Mianyang 621900 (China)

    2017-03-15

    A novel wavelength shifter of the 1,4-bis(4-methoxylstyryl)benzene (bis-4-MOSB) was synthesized by employing the classical Horner-Wadsworth-Emmons reaction. Feasible analysis of the bis-4-MOSB as the wavelength shifter in a ternary liquid scintillator, in which p-xylene (PX) was as the solvent and 2,5-diphenyloxazole (PPO) was as the primary fluor, was carried out. The optimum prescription with 3.5 g/L PPO and 25 mg/L bis-4-MOSB was obtained with regard to the light yield. A series of characterization tests based on the optimal formulation were performed. Compared with the 1,4-bis(2-methylstyryl)benzene (bis-MSB), the maximum absorption peak at 356 nm and maximum emission peak at 421 nm in n-hexane with the red shift of 10 nm and 3 nm, respectively, were measured accordingly. The light yield characterized by using a relative measurement method achieved as high as 75.85% of the anthracene crystal. A brief density functional calculation was conducted to have an insight into the electronic structure characteristic of the bis-4-MOSB in the scintillation process. - Graphic abstract: In our work, 1,4-bis(4-methoxylstyryl)benzene (bis-4-MOSB), as a novel wavelength shifter of liquid scintillator, was designed and synthesized. A comparison including absorption spectra and electronic structure characteristic between bis-4-MOSB and bis-MSB were conducted. Its maximum emission peak lied at 421 nm in n-hexane was corresponded to the maximum response range wavelength of PMT for the bis-4-MOSB. Furthermore, compared with the bis-MSB, the wavelength shifter of bis-4-MOSB showed a better luminescence performance.

  8. Theory and experiment studies of the 1,4-bis(4-methoxylstyryl)benzene as a wavelength shifter of liquid scintillator

    International Nuclear Information System (INIS)

    Zheng, Zhanlong; Zhu, Jiayi; Bi, Yutie; Xu, Yewei; Zhang, Qianfeng; Zhang, Xing; Li, Junjiang; Zhang, Lin

    2017-01-01

    A novel wavelength shifter of the 1,4-bis(4-methoxylstyryl)benzene (bis-4-MOSB) was synthesized by employing the classical Horner-Wadsworth-Emmons reaction. Feasible analysis of the bis-4-MOSB as the wavelength shifter in a ternary liquid scintillator, in which p-xylene (PX) was as the solvent and 2,5-diphenyloxazole (PPO) was as the primary fluor, was carried out. The optimum prescription with 3.5 g/L PPO and 25 mg/L bis-4-MOSB was obtained with regard to the light yield. A series of characterization tests based on the optimal formulation were performed. Compared with the 1,4-bis(2-methylstyryl)benzene (bis-MSB), the maximum absorption peak at 356 nm and maximum emission peak at 421 nm in n-hexane with the red shift of 10 nm and 3 nm, respectively, were measured accordingly. The light yield characterized by using a relative measurement method achieved as high as 75.85% of the anthracene crystal. A brief density functional calculation was conducted to have an insight into the electronic structure characteristic of the bis-4-MOSB in the scintillation process. - Graphic abstract: In our work, 1,4-bis(4-methoxylstyryl)benzene (bis-4-MOSB), as a novel wavelength shifter of liquid scintillator, was designed and synthesized. A comparison including absorption spectra and electronic structure characteristic between bis-4-MOSB and bis-MSB were conducted. Its maximum emission peak lied at 421 nm in n-hexane was corresponded to the maximum response range wavelength of PMT for the bis-4-MOSB. Furthermore, compared with the bis-MSB, the wavelength shifter of bis-4-MOSB showed a better luminescence performance.

  9. Asymmetric H-D exchange reactions of fluorinated aromatic ketones

    KAUST Repository

    Zhao, Yujun; Lim, XiaoZhi; Pan, Yuanhang; Zong, Lili; Feng, Wei; Tan, Choonhong; Huang, Kuo-Wei

    2012-01-01

    Chiral bicyclic guanidine catalyzes the asymmetric H-D exchange reactions. Up to 30% ee was achieved. DFT calculations were employed to elucidate and explain the origin of the reaction's stereoselectivity. © 2012 The Royal Society of Chemistry.

  10. Visual Hallucinations in a Patient with Horner's Syndrome Secondary to Internal Carotid Dissection

    OpenAIRE

    Amardeep Singh; Panteleimon Mortzos; Torben Lykke Sørensen

    2014-01-01

    A 67-year-old female presented with post-ganglionic Horner's syndrome. In addition to the classical symptoms of Horner's syndrome, the patient reported experiencing frightening complex visual and auditory hallucinations on two different occasions. Magnetic resonance angiography of the cerebrum, neck and upper thorax revealed internal carotid dissection. The symptoms and hallucinatory experiences resolved soon after antiplatelet therapy was commenced. We propose peduncular hallucinosis as the ...

  11. A Case of Horner's Syndrome following Ultrasound-Guided Infraclavicular Brachial Plexus Block.

    Science.gov (United States)

    Walid, Trabelsi; Mondher, Belhaj Amor; Mohamed Anis, Lebbi; Mustapha, Ferjani

    2012-01-01

    Horner's syndrome results from paralysis of the ipsilateral sympathetic cervical chain (stellate ganglion) caused by surgery, drugs (mainly high concentrations of local anesthetics), local compression (hematoma or tumor), or inadequate perioperative positioning of the patient. It occurs in 100% of the patients with an interscalene block of the brachial plexus and can also occur in patients with other types of supraclavicular blocks.In this case report, we presented a case of Horner's syndrome after performing an ultrasound-guided infraclavicular brachial plexus block with 15 mL of bupivacaine 0.5%. It appeared 40 minutes after the block with specific triad (ptosis, miosis, and exophtalmia) and quickly disappears within 2 hours and a half without any sequelae. Horner's syndrome may be described as an unpleasant side effect because it has no clinical consequences in itself. For this reason anesthesiologists should be aware of this syndrome, and if it occurs patients should be reassured and monitored closely.

  12. Rhabdomyolysis resulting in concurrent Horner's syndrome and brachial plexopathy: a case report

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Susan C.; Geannette, Christian; Sneag, Darryl B. [Hospital for Special Surgery, Department of Radiology and Imaging, New York, NY (United States); Wolfe, Scott W. [Hospital for Special Surgery, Hand and Upper Extremity, Department of Orthopedics, New York, NY (United States); Feinberg, Joseph H. [Hospital for Special Surgery, Physical Medicine and Rehabilitation, New York, NY (United States)

    2017-08-15

    This case report describes a 29-year-old male who presented with immediate onset of Horner's syndrome and ipsilateral brachial plexopathy after sleeping with his arm dangling outside a car window for 8 h. Outside workup and imaging revealed rhabdomyolysis of the left neck musculature. Subsequent electrodiagnostic testing and high-resolution brachial plexus magnetic resonance imaging at the authors' institution attributed the Horner's syndrome and concurrent brachial plexopathy to rhabdomyolysis of the longus colli and scalene musculature, which had compressed - and consequently scar tethered - the cervical sympathetic trunk and brachial plexus. This case of co-existent Horner's syndrome and brachial plexopathy demonstrates the role of high-resolution brachial plexus MRI in diagnosing plexopathy and the importance of being familiar with plexus and paravertebral muscle anatomy. (orig.)

  13. Metal-catalyzed Asymmetric Hetero-Diels-Alder Reactions of Unactivated Dienes with Glyoxylates

    DEFF Research Database (Denmark)

    Johannsen, Mogens; Yao, Sulan; Graven, Anette

    1998-01-01

    The development of a catalytic asymmetric hetero-Diels-Alder methodology for the reaction of unactivated dienes with glyoxylates is presented. Several different asymmetric catalysts can be used, but copper-bisoxazolines and aluminium-BINOL give the highest yield, and the best chemo...

  14. Imaging of Horner's syndrome

    Energy Technology Data Exchange (ETDEWEB)

    George, A.; Haydar, A.A. [Derriford Hospital Plymouth, Derriford, Plymouth (United Kingdom); Adams, W.M. [Derriford Hospital Plymouth, Derriford, Plymouth (United Kingdom)], E-mail: william.adams@phnt.swest.nhs.uk

    2008-05-15

    Horner's syndrome, or oculosympathetic paresis, results from interruption of the sympathetic trunk innervation to the eye and presents typically with meiosis, ptosis and facial anhydrosis on the affected side.{sup 1} The pathological process ranges from benign, such as cluster headache, or life threatening, such as lung malignancy. Appropriate imaging requires an anatomical appreciation of the complex and circuitous route the neuronal pathway takes as it passes from the central nervous system to the eye.

  15. Horner's syndrome caused by an intercostal chest drain.

    OpenAIRE

    Campbell, P; Neil, T; Wake, P N

    1989-01-01

    Horner's syndrome occurred in a young woman as a complication of the treatment of a traumatic pneumothorax with an intercostal drain. The nerve damage probably occurred when the lung had fully re-expanded, pressing the tip of the intercostal drain, lying at the apex of the pleural cavity, on to the sympathetic chain.

  16. Pharmacological testing in Horner's syndrome – a new paradigm ...

    African Journals Online (AJOL)

    For more than three decades, topical cocaine has been used to confirm the diagnosis and hydroxyamphetamine to localise the causative lesion in oculosympathetic palsy or Horner's syndrome. More recently, other drugs have demonstrated the ability to point to the diagnosis or anatomical site. Apraclonidine and ...

  17. Metal Chelation in Asymmetric Diels-Alder Reaction (II)

    International Nuclear Information System (INIS)

    Chung, Kyoo Hyun; Chu, Chan Kook; Chang, Min Ho

    2004-01-01

    In the reaction, the inverse asymmetric induction has been observed by the use of either monovalent Lewis acids or divalent Lewis acids. The reaction of the acrylate of (S)-ethyl lactate with cyclopentadiene proceeded with 86% endo-S selectivity in the presence of TiCl 4 , divalent Lewis acid, whereas did with 32% endo-R selectivity in the presence of BF 3 ·Et 2 O, monovalent Lewis acid. When a chiral dienophile which was prepared from benzyl ester of (S)-proline or methyl ester of (S)-indoline-2-carboxylic acid was employed in the reaction, a similar diastereofacial selectivity was also observed. Recently, we reported the similar selectivity in the reaction of methyl (2S,5S)-(5-t-butyldimethylsilyloxypiperidin- 2-yl)ethanoatewith cyclopentadiene.

  18. Asymmetric Stetter reactions catalyzed by thiamine diphosphate-dependent enzymes.

    Science.gov (United States)

    Kasparyan, Elena; Richter, Michael; Dresen, Carola; Walter, Lydia S; Fuchs, Georg; Leeper, Finian J; Wacker, Tobias; Andrade, Susana L A; Kolter, Geraldine; Pohl, Martina; Müller, Michael

    2014-12-01

    The intermolecular asymmetric Stetter reaction is an almost unexplored transformation for biocatalysts. Previously reported thiamine diphosphate (ThDP)-dependent PigD from Serratia marcescens is the first enzyme identified to catalyze the Stetter reaction of α,β-unsaturated ketones (Michael acceptor substrates) and α-keto acids. PigD is involved in the biosynthesis of the potent cytotoxic agent prodigiosin. Here, we describe the investigation of two new ThDP-dependent enzymes, SeAAS from Saccharopolyspora erythraea and HapD from Hahella chejuensis. Both show a high degree of homology to the amino acid sequence of PigD (39 and 51 %, respectively). The new enzymes were heterologously overproduced in Escherichia coli, and the yield of soluble protein was enhanced by co-expression of the chaperone genes groEL/ES. SeAAS and HapD catalyze intermolecular Stetter reactions in vitro with high enantioselectivity. The enzymes possess a characteristic substrate range with respect to Michael acceptor substrates. This provides support for a new type of ThDP-dependent enzymatic activity, which is abundant in various species and not restricted to prodigiosin biosynthesis in different strains. Moreover, PigD, SeAAS, and HapD are also able to catalyze asymmetric carbon-carbon bond formation reactions of aldehydes and α-keto acids, resulting in 2-hydroxy ketones.

  19. Horner's syndrome in patients admitted to the intensive care unit that have undergone central venous catheterization: a prospective study.

    Science.gov (United States)

    Butty, Z; Gopwani, J; Mehta, S; Margolin, E

    2016-01-01

    PurposeCentral venous catheterization (CVC) is estimated to be performed in millions of patients per year. Swan-Ganz catheters used for CVC are most often inserted into the internal jugular vein and during this procedure they may come into contact with the sympathetic chain. This study aims to determine the incidence of Horner's syndrome in patients admitted to intensive care unit that have undergone internal jugular CVC insertion during their admission and to determine whether ultrasonography-assisted insertion has decreased the frequency of this complication.Patients and methodsA total of 100 prospective patients admitted to the ICU were examined for the presence of anisocoria and ptosis after undergoing recent CVC. Presence of Horner's syndrome was confirmed by testing with 0.5% apraclonidine and looking for the reversal of anisocoria.ResultsFrequency of Horner's syndrome after CVC was 2% in a sample of 100 prospectively examined patients.ConclusionHorner's syndrome remains a relatively rare but definitive complication of CVC. ICU physicians should be educated about its existence and prevalence and ophthalmologists should inquire about any history of ICU admission necessitating CVC insertion in any patient presenting with Horner's syndrome.

  20. Leonard Horner and an enthusiasm for Loess. [Leicester Studies in the History of Loess Research part I

    Science.gov (United States)

    Smalley, Ian; Kels, Holger

    2018-04-01

    Leonard Horner (1785-1864) made substantial contributions to the study of loess. He made field trips with J.J. Noeggerath and Charles Lyell and published useful material on the loess near Bonn. He was an unappreciated pioneer- he was the first person to direct attention to loess as a material. He pointed out that loess was intrinsically interesting. He studied the material transported by the Rhine, and the alluvial deposits in Egypt, looking for links to loess, and the problem of loess formation. He was born in Edinburgh in 1785 and directed the thoughts of young Charles Darwin towards science when he came to Edinburgh to study medicine. Circumstances placed him in Bonn in the critical years 1831-1833; in this time Charles Lyell married his eldest daughter Mary; and both Lyell and Horner encountered the loess. Lyell made it well known via vol.3 of the Principles of Geology, Horner became a loess enthusiast. In the summer of 1833 Horner & Lyell were in the crater of the Roderberg considering the more than 20 m of loess deposited there. His major paper was published in 1836 (reporting the Roderberg excursion) and he joined Lyell's list of loess investigators in the 5th edition of the Principles published in 1837. He was the last to join that select eleven: Bronn, Leonhard, Boue, Voltz, Steininger, Merian, Rozet, Hibbert, Noeggerath, von Meyer, Horner. Most of these were writing on the geology and landscapes of the Rhine valley, but Horner was drawing attention to the amazing nature of the loess itself, in particular the spectacular disaggregation on contact with water. He also published the first geological map of the Bonn region, including the Roderberg and the Siebengebirge, a region of loess and volcanoes.

  1. Catalytic asymmetric diels-alder reaction of quinone imine ketals: a site-divergent approach.

    Science.gov (United States)

    Hashimoto, Takuya; Nakatsu, Hiroki; Maruoka, Keiji

    2015-04-07

    The catalytic asymmetric Diels-Alder reaction of quinone imine ketals with diene carbamates catalyzed by axially chiral dicarboxylic acids is reported herein. A variety of primary and secondary alkyl-substituted quinone derivatives which have not been applied in previous asymmetric quinone Diels-Alder reactions could be employed using this method. More importantly, we succeeded in developing a strategy to divert the reaction site in unsymmetrical 3-alkyl quinone imine ketals from the inherently favored unsubstituted C=C bond to the disfavored alkyl-substituted C=C bond. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Asymmetric Diels-Alder reactions with 5-menthyloxy-2(5H)-furanones

    NARCIS (Netherlands)

    Jong, Johannes Cornelis de

    2006-01-01

    At the beginning of the reseach described in this thesis the catalytic asymmetric Diels-Alder reaction had scarcely been investigated. No good catalytic processes with high enantiomeric excess were known at that time. At the same time the Diels-Alder reactions with chiral dienophiles needed further

  3. Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium

    Directory of Open Access Journals (Sweden)

    Pégot Bruce

    2006-09-01

    Full Text Available Abstract The asymmetric aza-Diels-Alder reaction of chiral imines with Danishefsky's diene in chiral ionic liquids provides the corresponding cycloadduct with moderate to high diastereoselectivity. The reaction has proved to perform better at room temperature in ionic liquids without either Lewis acid catalyst or organic solvent. Chiral ionic liquids are recycled while their efficiency is preserved.

  4. Asymmetry of salivary gland I123 Metaiodobenzylguanidine (MIBG) uptake in a patient with cervical neuroblastoma and Horner's syndrome - possible etiologic mechanisms

    International Nuclear Information System (INIS)

    Sandler, E.D.; Hattner, R.S.; Parisi, M.T.

    1992-01-01

    Horner's syndrome may be due to a variety of serious underlying disorders including cervical neuroblastoma. Horner's syndrome results from a unilateral disruption of the sympathetic innervation to the head and neck. We report a patient with cervical neuroblastoma in whom post operative metaiodobenzylguanidine (MIBG) scans showed a striking decrease in uptake in the ipselateral salivary glands. Since the biodistribution of I 123 metaiodobenzylguanidine in the salivary glands is also dependent on sympathetic innervation, the presence of Horner's syndrome can be reflected in the MIBG scan. (orig.)

  5. Unusual Horner's syndrome in recurrent breast cancer: Evaluating using {sup 18}F-FDG PET/CT

    Energy Technology Data Exchange (ETDEWEB)

    Park, So Hyun; Kim, Tae Sung; Kim, Seok Ki [Dept. of Nuclear Medicine, National Cancer Center, Goyang (Korea, Republic of)

    2017-03-15

    {sup 18}F-fluorodeoxyglucose (FDG) positron emission tomography/computed tomography (PET/CT) is a widely used imaging modality in the initial diagnosis of cancer, treatment response evaluation and detection of recurrence. Herein, we present the case of a 39-year-old female who presented right ptosis on the follow-up of breast cancer after surgery. Clinicians suspected Horner's syndrome, and the patient underwent FDG PET/CT for the evaluation of recurrence that could cause Horner's syndrome. FDG PET/CT demonstrated a focal hypermetabolic lesion in the right cervicothoracic junction area, corresponding to the preganglionic cervical sympathetic trunk. A subsequent needle biopsy was done, and the lesion was confirmed as metastatic ductal carcinoma. In this case, we could detect the exact location of the recurring lesion that caused Horner's syndrome using FDG PET/CT.

  6. Propulsion of a Molecular Machine by Asymmetric Distribution of Reaction Products

    Science.gov (United States)

    Golestanian, Ramin; Liverpool, Tanniemola B.; Ajdari, Armand

    2005-06-01

    A simple model for the reaction-driven propulsion of a small device is proposed as a model for (part of) a molecular machine in aqueous media. The motion of the device is driven by an asymmetric distribution of reaction products. The propulsive velocity of the device is calculated as well as the scale of the velocity fluctuations. The effects of hydrodynamic flow as well as a number of different scenarios for the kinetics of the reaction are addressed.

  7. Direct Enantioselective Reaction between Hemiacetals and Phosphorus Ylides: Important Role of a By-Product in the Asymmetric Transformation.

    Science.gov (United States)

    Wang, Rui; Wang, Linqing; Yang, Dongxu; Li, Dan; Liu, Xihong; Wang, Pengxin; Wang, Kezhou; Zhu, Haiyong; Bai, Lutao

    2018-05-16

    By employing a simple in-situ generated magnesium catalyst, the direct asymmetric reaction between hemiacetals and P-ylides is achieved via a tandem Wittig-oxa-Michael reaction sequence. Enantioenriched chromans, isochromans and tetrahydropyrans can be obtained in good chemical yields. (-)-Erythrococcamide B can be asymmetrically synthesized through this synthetic technique. In this work, the by-product, TPO, was identified as a necessary additive in this asymmetric synthetic method. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Asymmetric fission of 47V induced by the 23Na+24Mg reaction

    International Nuclear Information System (INIS)

    Beck, C.; Djerroud, B.; Haas, F.; Freeman, R.M.; Hachem, A.; Heusch, B.; Morsad, A.; Vuillet-A-Cilles, M.; Sanders, S.J.

    1993-01-01

    The properties of fully energy-damped processes (deep-inelastic orbiting, fusion-evaporation, and fusion-fission processes) have been investigated in the nearly mass-symmetric entrance-channel 23 Na + 24 Mg reaction leading to the 47 V compound nucleus. By comparison with previous data for the mass-asymmetric 35 Cl + 12 C reaction forming the same compound system at the same excitation energy, no entrance-channel effects are observed in either the evaporation residue or the fusion-fission yields. This is in contrast to the situation with the 28 Si + 12 C and 24 Mg + 16 O reactions where an orbiting process is evident. The asymmetrical elemental distributions of the fusion-fission fragments of the massA=47 system are well described by a transition-state model that accounts for the spin and mass-asymmetry dependence of the fission saddle point

  9. Temperamental workers: Psychology, business, and the Humm-Wadsworth Temperament Scale in interwar America.

    Science.gov (United States)

    Lussier, Kira

    2018-05-01

    This article traces the history of a popular interwar psychological test, the Humm-Wadsworth Temperament Scale (HWTS), from its development in the early 1930s to its adoption by corporate personnel departments. In popular articles, trade magazines, and academic journals, industrial psychologist Doncaster Humm and personnel manager Guy Wadsworth trumpeted their scale as a scientific measure of temperament that could ensure efficient hiring practices and harmonious labor relations by screening out "problem employees" and screening for temperamentally "normal" workers. This article demonstrates how concerns about the epistemological and scientific credibility of the HWTS were intimately entangled with concerns about its value to business at every step in the test's development. The HWTS sought to measure the emotional and social dimensions of an individual's personality so as to assess their suitability for work. The practice of temperament testing conjured a vision of the subject whose emotional and social disposition was foundational to their own capacity to find employment, and whose capacity to appropriately express, but regulate, their emotions was foundational to corporate order. The history of the HWTS offers an instructive case of how psychological tests embed social hierarchies, political claims, and economic ideals within their very theoretical and methodological foundations. Although the HWTS itself may have faded from use, the test directly inspired creators of subsequent popular personality tests, such as the Minnesota Multiphasic Personality Inventory and the Myers-Briggs Type Indicator. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

  10. Practical spectrophotometric assay for the dapE-encoded N-succinyl-L,L-diaminopimelic acid desuccinylase, a potential antibiotic target.

    Science.gov (United States)

    Heath, Tahirah K; Lutz, Marlon R; Reidl, Cory T; Guzman, Estefany R; Herbert, Claire A; Nocek, Boguslaw P; Holz, Richard C; Olsen, Kenneth W; Ballicora, Miguel A; Becker, Daniel P

    2018-01-01

    A new enzymatic assay for the bacterial enzyme succinyl-diaminopimelate desuccinylase (DapE, E.C. 3.5.1.18) is described. This assay employs N6-methyl-N2-succinyl-L,L-diaminopimelic acid (N6-methyl-L,L-SDAP) as the substrate with ninhydrin used to detect cleavage of the amide bond of the modified substrate, wherein N6-methylation enables selective detection of the primary amine enzymatic product. Molecular modeling supported preparation of the mono-N6-methylated-L,L-SDAP as an alternate substrate for the assay, given binding in the active site of DapE predicted to be comparable to the endogenous substrate. The alternate substrate for the assay, N6-methyl-L,L-SDAP, was synthesized from the tert-butyl ester of Boc-L-glutamic acid employing a Horner-Wadsworth-Emmons olefination followed by an enantioselective reduction employing Rh(I)(COD)(S,S)-Et-DuPHOS as the chiral catalyst. Validation of the new ninhydrin assay was demonstrated with known inhibitors of DapE from Haemophilus influenza (HiDapE) including captopril (IC50 = 3.4 [± 0.2] μM, 3-mercaptobenzoic acid (IC50 = 21.8 [±2.2] μM, phenylboronic acid (IC50 = 316 [± 23.6] μM, and 2-thiopheneboronic acid (IC50 = 111 [± 16] μM. Based on these data, this assay is simple and robust, and should be amenable to high-throughput screening, which is an important step forward as it opens the door to medicinal chemistry efforts toward the discovery of DapE inhibitors that can function as a new class of antibiotics.

  11. Practical spectrophotometric assay for the dapE-encoded N-succinyl-L,L-diaminopimelic acid desuccinylase, a potential antibiotic target.

    Directory of Open Access Journals (Sweden)

    Tahirah K Heath

    Full Text Available A new enzymatic assay for the bacterial enzyme succinyl-diaminopimelate desuccinylase (DapE, E.C. 3.5.1.18 is described. This assay employs N6-methyl-N2-succinyl-L,L-diaminopimelic acid (N6-methyl-L,L-SDAP as the substrate with ninhydrin used to detect cleavage of the amide bond of the modified substrate, wherein N6-methylation enables selective detection of the primary amine enzymatic product. Molecular modeling supported preparation of the mono-N6-methylated-L,L-SDAP as an alternate substrate for the assay, given binding in the active site of DapE predicted to be comparable to the endogenous substrate. The alternate substrate for the assay, N6-methyl-L,L-SDAP, was synthesized from the tert-butyl ester of Boc-L-glutamic acid employing a Horner-Wadsworth-Emmons olefination followed by an enantioselective reduction employing Rh(I(COD(S,S-Et-DuPHOS as the chiral catalyst. Validation of the new ninhydrin assay was demonstrated with known inhibitors of DapE from Haemophilus influenza (HiDapE including captopril (IC50 = 3.4 [± 0.2] μM, 3-mercaptobenzoic acid (IC50 = 21.8 [±2.2] μM, phenylboronic acid (IC50 = 316 [± 23.6] μM, and 2-thiopheneboronic acid (IC50 = 111 [± 16] μM. Based on these data, this assay is simple and robust, and should be amenable to high-throughput screening, which is an important step forward as it opens the door to medicinal chemistry efforts toward the discovery of DapE inhibitors that can function as a new class of antibiotics.

  12. A Ligand Structure-Activity Study of DNA-Based Catalytic Asymmetric Hydration and Diels-Alder Reactions

    NARCIS (Netherlands)

    Rosati, F.; Roelfes, J.G.

    A structure-activity relationship study of the first generation ligands for the DNA-based asymmetric hydration of enones and Diels-Alder reaction in water is reported. The design of the ligand was optimized resulting in a maximum ee of 83% in the hydration reaction and 75% in the Diels-Alder

  13. A nanojet: propulsion of a molecular machine by an asymmetric distribution of reaction--products

    Science.gov (United States)

    Liverpool, Tanniemola; Golestanian, Ramin; Ajdari, Armand

    2006-03-01

    A simple model for the reaction-driven propulsion of a small device is proposed as a model for (part of) a molecular machine in aqueous media. Motion of the device is driven by an asymmetric distribution of reaction products. We calculate the propulsive velocity of the device as well as the scale of the velocity fluctuations. We also consider the effects of hydrodynamic flow as well as a number of different scenarios for the kinetics of the reaction.

  14. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

    KAUST Repository

    Stoltz, Brian

    2010-06-14

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  15. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

    KAUST Repository

    Stoltz, Brian; McDougal, Nolan; Virgil, Scott

    2010-01-01

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  16. Principles of asymmetric synthesis

    CERN Document Server

    Gawley, Robert E; Aube, Jeffrey

    2012-01-01

    The world is chiral. Most of the molecules in it are chiral, and asymmetric synthesis is an important means by which enantiopure chiral molecules may be obtained for study and sale. Using examples from the literature of asymmetric synthesis, this book presents a detailed analysis of the factors that govern stereoselectivity in organic reactions. After an explanation of the basic physical-organic principles governing stereoselective reactions, the authors provide a detailed, annotated glossary of stereochemical terms. A chapter on "Practical Aspects of Asymmetric Synthesis" provides a critical overview of the most common methods for the preparation of enantiomerically pure compounds, techniques for analysis of stereoisomers using chromatographic, spectroscopic, and chiroptical methods. The authors then present an overview of the most important methods in contemporary asymmetric synthesis organized by reaction type. Thus, there are four chapters on carbon-carbon bond forming reactions, one chapter on reductions...

  17. Catalytic Asymmetric Total Synthesis of (+)- and (-)-Paeoveitol via a Hetero-Diels-Alder Reaction.

    Science.gov (United States)

    Li, Tian-Ze; Geng, Chang-An; Yin, Xiu-Juan; Yang, Tong-Hua; Chen, Xing-Long; Huang, Xiao-Yan; Ma, Yun-Bao; Zhang, Xue-Mei; Chen, Ji-Jun

    2017-02-03

    The first catalytic asymmetric total synthesis of (+)- and (-)-paeoveitol has been accomplished in 42% overall yield via a biomimetic hetero-Diels-Alder reaction. The chiral phosphoric acid catalyzed hetero-Diels-Alder reaction showed excellent diastereo- and enantioselectivity (>99:1 dr and 90% ee); two rings and three stereocenters were constructed in a single step to produce (-)-paeoveitol on a scale of 452 mg. This strategy enabled us to selectively synthesize both paeoveitol enantiomers from the same substrates by simply changing the enantiomer of the catalyst.

  18. Asymmetric Formal Aza-Diels-Alder Reaction of Trifluoromethyl Hemiaminals with Enones Catalyzed by Primary Amines.

    Science.gov (United States)

    Zhang, Sheng; Cha, Lide; Li, Lijun; Hu, Yanbin; Li, Yanan; Zha, Zhenggen; Wang, Zhiyong

    2016-04-15

    A primary amine-catalyzed asymmetric formal aza-Diels-Alder reaction of trifluoromethyl hemiaminals with enones was developed via a chiral gem-diamine intermediate. This novel protocol allowed facile access to structurally diverse trifluoromethyl-substituted piperidine scaffolds with high stereoselectivity. The utility of this method was further demonstrated through a concise approach to biologically active 4-hydroxypiperidine. More importantly, a stepwise mechanism involving an asymmetric induction process was proposed to rationalize the positive correlation between the chirality of the gem-diamine intermediate and the formal aza-Diels-Alder product.

  19. Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions

    KAUST Repository

    Benhamou, Laure

    2014-01-13

    PEPPSI complexes incorporating chiral N-heterocyclic carbene (NHC) ligands based on 2,2-dimethyl-1-(o-substituted aryl)propan-1-amines were synthesized. Two complexes, with one saturated and one unsaturated NHC ligand, were structurally characterized. The chiral PEPPSI complexes were used in asymmetric Suzuki-Miyaura reactions, giving atropisomeric biaryl products in modest to good enantiomeric ratios. © 2013 American Chemical Society.

  20. Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions

    KAUST Repository

    Benhamou, Laure; Besnard, Cé line; Kü ndig, E. Peter

    2014-01-01

    PEPPSI complexes incorporating chiral N-heterocyclic carbene (NHC) ligands based on 2,2-dimethyl-1-(o-substituted aryl)propan-1-amines were synthesized. Two complexes, with one saturated and one unsaturated NHC ligand, were structurally characterized. The chiral PEPPSI complexes were used in asymmetric Suzuki-Miyaura reactions, giving atropisomeric biaryl products in modest to good enantiomeric ratios. © 2013 American Chemical Society.

  1. Asymmetric Catalytic Aza-Diels-Alder/Ring-Closing Cascade Reaction Forming Bicyclic Azaheterocycles by Trienamine Catalysis.

    Science.gov (United States)

    Li, Yang; Barløse, Casper; Jørgensen, Julie; Carlsen, Bjørn Dreiø; Jørgensen, Karl Anker

    2017-01-01

    An asymmetric catalytic aza-Diels-Alder/ring-closing cascade reaction between acylhydrazones and in situ formed trienamines is presented. The reaction proceeds through a formal aza-Diels-Alder cycloaddition, followed by a ring-closing reaction forming the hemiaminal ring leading to chiral bicyclic azaheterocycles in moderate to good yield (up to 71 %), good enantio- (up to 92 % ee) and diastereoselectivity (up to >20:1 d.r.). Furthermore, transformations are presented to show the potential application of the formed product. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Correction: Synthesis of pyrrolidine-3-carboxylic acid derivatives via asymmetric Michael addition reactions of carboxylate-substituted enones.

    Science.gov (United States)

    Yin, Feng; Garifullina, Ainash; Tanaka, Fujie

    2018-04-25

    Correction for 'Synthesis of pyrrolidine-3-carboxylic acid derivatives via asymmetric Michael addition reactions of carboxylate-substituted enones' by Feng Yin et al., Org. Biomol. Chem., 2017, 15, 6089-6092.

  3. Enantioselective syntheses and biological studies of aeruginosin 298-A and its analogs: application of catalytic asymmetric phase-transfer reaction.

    Science.gov (United States)

    Fukuta, Yuhei; Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Nemoto, Tetsuhiro; Kisugi, Takaya; Okino, Tatsufumi; Shibasaki, Masakatsu

    2004-04-13

    Aeruginosin 298-A was isolated from the freshwater cyanobacterium Microcystis aeruginosa (NIES-298) and is an equipotent thrombin and trypsin inhibitor. A variety of analogs were synthesized to gain insight into the structure-activity relations. We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogs, in which all stereocenters were controlled by catalytic asymmetric phase-transfer reaction promoted by two-center asymmetric catalysts and catalytic asymmetric epoxidation promoted by a lanthanide-BINOL complex. Furthermore, serine protease inhibitory activities of aeruginosin 298-A and its analogs were examined.

  4. Neuromyelitis optica presenting with horner syndrome: A case report and review of literature.

    Science.gov (United States)

    Uludağ, İrem Fatma; Sarıteke, Alp; Öcek, Levent; Zorlu, Yaşar; Şener, Ufuk; Tokuçoğlu, Figen; Uludağ, Burhanettin

    2017-05-01

    Neuromyelitis optica (NMO) is a demyelinating disease of the central nervous system that predominantly affects the spinal cord and optic nerves. We describe a 19 years old woman with left Horner syndrome (HS), who was diagnosed as NMO with characteristic longitudinally extensive myelitis and positive serum aquaporin-4 immunoglobulin G antibodies (AQP4-IgG). Our report describes one of the very rare ocular motor symptoms in NMO patients. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Brain-computer interface signal processing at the Wadsworth Center: mu and sensorimotor beta rhythms.

    Science.gov (United States)

    McFarland, Dennis J; Krusienski, Dean J; Wolpaw, Jonathan R

    2006-01-01

    The Wadsworth brain-computer interface (BCI), based on mu and beta sensorimotor rhythms, uses one- and two-dimensional cursor movement tasks and relies on user training. This is a real-time closed-loop system. Signal processing consists of channel selection, spatial filtering, and spectral analysis. Feature translation uses a regression approach and normalization. Adaptation occurs at several points in this process on the basis of different criteria and methods. It can use either feedforward (e.g., estimating the signal mean for normalization) or feedback control (e.g., estimating feature weights for the prediction equation). We view this process as the interaction between a dynamic user and a dynamic system that coadapt over time. Understanding the dynamics of this interaction and optimizing its performance represent a major challenge for BCI research.

  6. Enhancement of nuclear reaction rates in asymmetric binary ionic mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Clerouin, J.; Arnault, P.; Desbiens, N. [CEA, DAM, DIF, Arpajon (France); White, A.; Ticknor, C.; Kress, J.D.; Collins, L.A. [Theoretical Division, Los Alamos National Laboratory, Los Alamos, NM (United States)

    2017-11-15

    Using orbital-free molecular dynamics simulations we study the structure and dynamics of increasingly asymmetric mixtures such as hydrogen-carbon, hydrogen-aluminium, hydrogen-copper, and hydrogen-silver. We show that, whereas the heavy component structure is close to an effective one-component plasma (OCP), the light component appears more structured than the corresponding OCP. This effect is related to the crossover towards a Lorentz-type diffusion triggered by strongly coupled, highly charged heavy ions, and witnessed by the change of temperature scaling laws of diffusion. This over-correlation translates into an enhancement of nuclear reaction rates much higher than its classical OCP counterpart. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. 1,2- and 1,3-dihydroxylated and hydroxynitrogenated monoterpenes as chiral ligands in the asymmetric reformatsky reaction

    International Nuclear Information System (INIS)

    Ribeiro, Carlos Magno R.; Morita, Cristina M.; Maia, Monica P.

    2008-01-01

    This study describes the use of three (-)-α-pinene derivatives, one diol-1,2 [(-)- (1R, 2R, 3S, 5R)-2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diol 4] and two pyridine-hydroxy derivatives [(+)-(1R,2S,3R,5S)-2,6,6- trimethyl-3-(2-pyridinylmethyl)bicyclo[3.1.1]heptane-3-ol 7 and (-)-(1R,2S,3R,5S)-2,6,6-trimethyl-3-[2-(2-pyridinyl) ethyl]bicyclo[3.1.1]heptane-3-ol 8]; one diol-1,3 [(-)-(1S,2R,5S)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanol 5] derived from (+)-isopulegol 2 and one diol-1,3 [(+)-(1R,2R,5R)-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanol 6] derived from (+)-neoisopulegol 3, as ligands in the asymmetric Reformatsky reaction. The best enantiomeric excess of β-hydroxy ester obtained in the Reformatsky asymmetric reaction was 18% using ligand 6, and the chemical yield of the reactions was 65% on average. (author)

  8. Síndrome de Horner na infância: relato de caso

    Directory of Open Access Journals (Sweden)

    Shiratori Claudia Akemi

    2004-01-01

    Full Text Available O intuito deste é apresentar um caso raro de síndrome de Horner na infância. Trata-se de uma criança do sexo masculino, com idade de 2 anos e 1 mês, que apresentava desde o nascimento ptose palpebral, miose e anidrose da hemiface esquerda. A instilação de fenilefrina 2,5% provocou midríase, com pupilas isocóricas, confirmando o diagnóstico. A história e o exame clínico auxiliam a localizar o nível da lesão e a estabelecer a etiologia do quadro.

  9. Multicatalyst system in asymmetric catalysis

    CERN Document Server

    Zhou, Jian

    2014-01-01

    This book introduces multi-catalyst systems by describing their mechanism and advantages in asymmetric catalysis.  Helps organic chemists perform more efficient catalysis with step-by-step methods  Overviews new concepts and progress for greener and economic catalytic reactions  Covers topics of interest in asymmetric catalysis including bifunctional catalysis, cooperative catalysis, multimetallic catalysis, and novel tandem reactions   Has applications for pharmaceuticals, agrochemicals, materials, and flavour and fragrance

  10. Skin vasomotor hemiparesis followed by overactivity: characteristic thermography findings in a patient with Horner syndrome due to spinal cord infarction.

    Science.gov (United States)

    Kobayashi, Makoto

    2016-04-01

    We present a 21-year-old female with Horner syndrome due to spinal cord infarction. In this patient, infrared thermography revealed a hemibody skin temperature increase followed by excessive focal decreases, indicating skin vasomotor hemiparesis and overactivity.

  11. Application of Carbohydrate-Templated Asymmetric Diels-Alder Reaction to the Syntheses of ent-Penicillones A and B.

    Science.gov (United States)

    Weng, Chia-Hao; Hsu, Day-Shin; Liao, Chun-Chen

    2016-11-18

    Total syntheses of ent-penicillones A (ent-1) and B (ent-2) from 3,5-dimethylcatechol (3) were accomplished in 10 and 9 synthetic steps, respectively. A carbohydrate-templated asymmetric intramolecular Diels-Alder reaction of a masked o-benzoquinone (MOB) 9 and an aqueous acid-catalyzed intramolecular aldol reaction are the key synthetic steps. In addition, the absolute configurations of the bicyclo[2.2.2]oct-5-en-2-one core obtained from the per-O-benzylated α-d-glucopyranosyl as a carbohydrate template in the intramolecular Diels-Alder reaction of MOBs were revised.

  12. Linear regression analysis of potentiometric titration data for asymmetric redox reactions

    International Nuclear Information System (INIS)

    Mar'yanov, B.M.; Gavrilenko, M.A.

    1997-01-01

    A statistical method of processing the curves of potentiometric titration for homogeneous asymmetric redox reactions has been suggested. The method was tested using a model titrimetric system Mohr's salt-K 2 Cr 2 O 7 and was employed for Te determination in an individual solution, semiconductor alloy and CdTe ceramics. Random error of the equivalence point evaluation by the data of a specific titration of 0.1-0.01 M solutions does not exceed 0.3% in case of titration of 0.001 M solutions it increases up to 1.2%. The value of s r varies from 0.0006 to 0.007

  13. Cinchona alkaloids in asymmetric organocatalysis

    NARCIS (Netherlands)

    Marcelli, T.; Hiemstra, H.

    2010-01-01

    This article reviews the applications of cinchona alkaloids as asymmetric catalysts. In the last few years, characterized by the resurgence of interest in asymmetric organocatalysis, cinchona derivatives have been shown to catalyze an outstanding array of chemical reactions, often with remarkable

  14. Probing short-range correlations in asymmetric nuclei with quasi-free pair knockout reactions

    Science.gov (United States)

    Stevens, Sam; Ryckebusch, Jan; Cosyn, Wim; Waets, Andreas

    2018-02-01

    Short-range correlations (SRC) in asymmetric nuclei with an unusual neutron-to-proton ratio can be studied with quasi-free two-nucleon knockout processes following the collision between accelerated ions and a proton target. We derive an approximate factorized cross section for those SRC-driven p (A ,p‧N1N2) reactions. Our reaction model hinges on the factorization properties of SRC-driven A (e ,e‧N1N2) reactions for which strong indications are found in theory-experiment comparisons. In order to put our model to the test we compare its predictions with results of 12C (p ,p‧ pn) measurements conducted at Brookhaven National Laboratory (BNL) and find a fair agreement. The model can also reproduce characteristic features of SRC-driven two-nucleon knockout reactions, like back-to-back emission of the correlated nucleons. We study the asymmetry dependence of nuclear SRC by providing predictions for the ratio of proton-proton to proton-neutron knockout cross sections for the carbon isotopes 9-15C thereby covering neutron excess values (N - Z) / Z between -0.5 and +0.5.

  15. Dynamic structural change of the self-assembled lanthanum complex induced by lithium triflate for direct catalytic asymmetric aldol-Tishchenko reaction.

    Science.gov (United States)

    Horiuchi, Yoshihiro; Gnanadesikan, Vijay; Ohshima, Takashi; Masu, Hyuma; Katagiri, Kosuke; Sei, Yoshihisa; Yamaguchi, Kentaro; Shibasaki, Masakatsu

    2005-09-05

    The development of a direct catalytic asymmetric aldol-Tishchenko reaction and the nature of its catalyst are described. An aldol-Tishchenko reaction of various propiophenone derivatives with aromatic aldehydes was promoted by [LaLi3(binol)3] (LLB), and reactivity and enantioselectivity were dramatically enhanced by the addition of lithium trifluoromethanesulfonate (LiOTf). First, we observed a dynamic structural change of LLB by the addition of LiOTf using 13C NMR spectroscopy, electronspray ionization mass spectrometry (ESI-MS), and cold-spray ionization mass spectrometry (CSI-MS). X-ray crystallography revealed that the structure of the newly generated self-assembled complex was a binuclear [La2Li4(binaphthoxide)5] complex 6. A reverse structural change of complex 6 to LLB by the addition of one equivalent of Li2(binol) was also confirmed by ESI-MS and experimental results. The drastic concentration effects on the direct catalytic asymmetric aldol-Tishchenko reaction suggested that the addition of LiOTf to LLB generated an active oligomeric catalyst species.

  16. Organoplatinum complex promoted the asymmetric endo stereochemically controlled Diels-Alder reaction between 3-diphenylphosphinofuran and diphenylvinylphosphine.

    Science.gov (United States)

    Liu, Fengli; Pullarkat, Sumod A; Tan, Kien-Wee; Li, Yongxin; Leung, Pak-Hing

    2009-12-07

    The organoplatinum complex containing ortho-metalated (R)-(1-(dimethylamino)ethyl)-naphthalene as the chiral auxiliary has been used efficiently to promote the asymmetric [4 + 2] Diels-Alder reaction between diphenylvinylphosphine and 3-diphenylphosphinofuran to generate two chelating diphosphine endocycloadducts in the ratio 17:1. The absolute configurations of the three newly generated stereocenters have been assigned by single-crystal X-ray analysis.

  17. Health-hazard evaluation report HETA 86-456-1877, South Texas Nuclear Project, Wadsworth, Texas

    International Nuclear Information System (INIS)

    Sinks, T.H.; Hartle, R.W.

    1988-03-01

    An evaluation was made of an outbreak of dermatitis among workers at the South Texas Nuclear Project construction site, Wadsworth, Texas. The dermatitis occurred ten times more frequently among carpenters than other laborers, with the incidence in 1986 being 250% greater than it was in 1985. Some workers demonstrated pruritic, macular/papular lesions. Carpenters working on the inside of the power-project buildings had a higher incidence of skin disease than those employed on the outside of the buildings. Samples of plywood and lumber treated with fire-retardant indicated that they contained 3 and 5% phosphate, respectively. Arsenic was not detected but formaldehyde was detected at 59 parts per million. General environmental air samples were taken with no evidence found of airborne phosphate, melamine, dicyandiamide, or formaldehyde. Concentrations of total particulates ranged from 0.1 to 0.6mg/m 3 . The authors conclude that the workers were probably suffering from a contact dermatitis. The authors recommend specific precautions

  18. Using chiral ionic liquid additives to enhance asymmetric induction in a Diels-Alder reaction.

    Science.gov (United States)

    Goodrich, P; Nimal Gunaratne, H Q; Hall, L; Wang, Y; Jin, L; Muldoon, M J; Ribeiro, A P C; Pombeiro, A J L; Pârvulescu, V I; Davey, P; Hardacre, C

    2017-01-31

    A bis-oxazoline ligand has been complexed using Cu(ii) and Zn(ii) trifluoromethanesulfonate and a range of chiral ionic liquid (CIL) additives based on natural products were used as a co-catalyst for a Diels-Alder reaction. The catalytic performance of these systems was compared for the asymmetric Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene with and without the presence of a CIL additive. In the absence of the CIL, both catalysts resulted in low enantioselectivities in conventional solvents and ionic liquids. However, whilst only a minor effect of the CIL was observed for the Cu based catalyst, in the case of the Zn based catalyst, significant enhancements in endo enantioselectivity of up to 50% were found on the addition of a CIL.

  19. Asymmetric Construction of Benzindoloquinolizidine: Application of An Organocatalytic Enantioselective Conjugate Addition-Cyclization Cascade Reaction

    International Nuclear Information System (INIS)

    Kim, Cheolwoong; Seo, Seung Woo; Lee, Yona; Kim, Sunggon

    2014-01-01

    We have developed the synthetic methodology of enantioenriched benzindoloquinolizidines based on the organocatalytic enantioselective conjugate addition-cyclization cascade reaction of o-N-(3-indoleacetyl)amino-cinnamaldehydes with malonates followed by an acid-catalyzed intramolecular Pictet-Spengler type cyclization. The asymmetric reaction using diphenylprolinol TMS ether as an organocatalyst produces the desired products with good to excellent yields and high enantioselectivities (up to 98% ee). The evaluation of the applications of this synthetic methodology for generating enantioenriched benzindolo-quinolizidines and studies on the biological activity of these compounds against human prostate cancer in particular are now in progress. Results of these studies will be presented in due course. Many new types of chemical reactions have been developed to facilitate easier synthesis of complex compounds. Among the strategies, domino reactions, which have been utilized for the efficient and stereoselective construction of complex molecules from simple precursors in a single process, are widely used due to their high synthetic efficiency by reducing both the number of synthetic operation required and the quantities of chemicals and solvents used

  20. Multiplicity and asymmetric fireballs from π+p, K+p, γp, e-p, and μ-p reactions

    International Nuclear Information System (INIS)

    Hoang, T.F.; Chew, C.K.; Phua, K.K.

    1979-01-01

    Negative-pion multiplicities produced by asymmetric fireballs are investigated in terms of the fireball mass M*, related to the Feynman-Yang scaling. Assuming approx. M* and making use of results of the previous analysis on pp and p-barp data, it is found that only one parameter is needed for both π + p and K + p reactions and another one for γp, e - p, and μ - p reactions. An attempt is made to analyze π production by e + e - in analogy with the analysis of p-barp annihilation in a previous work

  1. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong

    2017-01-01

    The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts' solubility in conventional organic...... solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation-binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL-based polyethers. Alkali metal salts, namely KF...... highly enantioselective silylation reactions in polyether-generated chiral environments, and leading to a record-high turnover in asymmetric organocatalysis. This can lead to further applications by the asymmetric use of other inorganic salts in various organic transformations....

  2. Cyclodextrins in Asymmetric and Stereospecific Synthesis

    Directory of Open Access Journals (Sweden)

    Fliur Macaev

    2015-09-01

    Full Text Available Since their discovery, cyclodextrins have widely been used as green and easily available alternatives to promoters or catalysts of different chemical reactions in water. This review covers the research and application of cyclodextrins and their derivatives in asymmetric and stereospecific syntheses, with their division into three main groups: (1 cyclodextrins promoting asymmetric and stereospecific catalysis in water; (2 cyclodextrins’ complexes with transition metals as asymmetric and stereospecific catalysts; and (3 cyclodextrins’ non-metallic derivatives as asymmetric and stereospecific catalysts. The scope of this review is to systematize existing information on the contribution of cyclodextrins to asymmetric and stereospecific synthesis and, thus, to facilitate further development in this direction.

  3. Neuropharmacological lesion localization in idiopathic Horner's syndrome in Golden Retrievers and dogs of other breeds.

    Science.gov (United States)

    Simpson, Katherine M; Williams, David L; Cherubini, Giunio B

    2015-01-01

    To investigate whether idiopathic Horner's syndrome (HS) in Golden Retrievers is an exclusively preganglionic disorder based on denervation hypersensitivity pharmacological testing with phenylephrine. Medical records of dogs presented with HS between 2000 and 2012. Dogs presented with additional ocular or systemic signs were excluded. Clinical data examined included age, sex, duration of clinical signs, ancillary diagnostic test results, and time to mydriasis on topical ocular application of 1% phenylephrine. Lesions were diagnosed as postganglionic (mydriasis within 20 min) or preganglionic (mydriasis between 20 and 45 min). Medical records of 21 dogs of nine different breeds were included. An etiopathogenesis for Horner's syndrome was determined in five dogs, none of which were Golden Retrievers. All diagnoses correlated with pharmacological lesion localization. Ten Golden Retrievers were included (eight male and two female) with a mean age of 8.5 years (range: 4-13). Lesion localization was diagnosed as postganglionic in eight (mean: 10 min [range: 6-18]) and preganglionic in two Golden Retrievers (20 and 24 min). All cases were unilateral and had completely resolved within 15 weeks (range: 11-20). Recurrence was not reported in any of the patients. Idiopathic postganglionic HS was diagnosed in eight of 10 Golden Retrievers contradicting previous reports of a purely preganglionic localization. Etiopathogenesis of canine idiopathic HS remains to be determined; nevertheless, a vascular etiology cannot be excluded. Future studies using magnetic resonance angiography may aid in clarifying the pathogenesis. © 2013 American College of Veterinary Ophthalmologists.

  4. Impact of Secondary Interactions in Asymmetric Catalysis

    OpenAIRE

    Frölander, Anders

    2007-01-01

    This thesis deals with secondary interactions in asymmetric catalysis and their impact on the outcome of catalytic reactions. The first part revolves around the metal-catalyzed asymmetric allylic alkylation reaction and how interactions within the catalyst affect the stereochemistry. An OH–Pd hydrogen bond in Pd(0)–π-olefin complexes of hydroxy-containing oxazoline ligands was identified by density functional theory computations and helped to rationalize the contrasting results obtained emplo...

  5. Asymmetric Frontal Brain Activity and Parental Rejection

    NARCIS (Netherlands)

    Huffmeijer, R.; Alink, L.R.A.; Tops, M.; Bakermans-Kranenburg, M.J.; van IJzendoorn, M.H.

    2013-01-01

    Asymmetric frontal brain activity has been widely implicated in reactions to emotional stimuli and is thought to reflect individual differences in approach-withdrawal motivation. Here, we investigate whether asymmetric frontal activity, as a measure of approach-withdrawal motivation, also predicts

  6. Chiral 1,3,2-oxazaborolidines in asymmetric synthesis: recent advances

    International Nuclear Information System (INIS)

    Glushkov, Vladimir A; Tolstikov, Alexander G

    2004-01-01

    The use of chiral 1,3,2-oxazaborolidines in asymmetric organic synthesis, particularly, in enantioselective reduction of ketones, imines and oxime ethers, asymmetric Diels-Alder reactions, aldol condensation and atroposelective reduction of lactones is reviewed. Reactions of immobilised 1,3,2-oxazaborolidines are also considered.

  7. Asymmetric Benzylic Allylic Alkylation Reaction of 3-Furfural Derivatives by Dearomatizative Dienamine Activation.

    Science.gov (United States)

    He, Xiao-Long; Zhao, Hui-Ru; Duan, Chuan-Qi; Han, Xu; Du, Wei; Chen, Ying-Chun

    2018-04-20

    The dearomatizative dienamine-type ortho-quinodimethane species are smoothly generated between 2-alkyl-3-furfurals and chiral secondary amine catalysts, which undergo asymmetric benzylic allylic alkylation reactions with 2-nitroallylic acetates efficiently. A spectrum of densely functionalized 3-furfural derivatives are delivered in moderate to high yields with good to excellent diastereo- and enantioselectivity (up to 98 % yield, >19:1 d.r., >99 % ee). The latent transformations allow the facile production of some enantioenriched architectures, such as 1,1,2,2-tetraarylethanes and triarylmethanes, which are not easily available from other protocols. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. An Efficient Procedure Based on a MW-Assisted Horner–Wadsworth-Emmons Reaction for the Synthesis of (Z-3,3-Trisubstituted-a,b-unsaturated Esters

    Directory of Open Access Journals (Sweden)

    Ornella Azzolina

    2010-08-01

    Full Text Available A microwave-assisted HWE olefination process of readily accessible aryl-alkyl ketones has been developed to provide a rapid access to (Z-3,3-trisubstituted-α,β-unsaturated methyl esters, key building blocks for the synthesis of biologically active compounds.

  9. Metal-catalyzed asymmetric aldol reactions

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Luiz C.; Lucca Junior, Emilio C. de; Ferreira, Marco A. B.; Polo, Ellen C., E-mail: ldias@iqm.unicamp.br [Universidade de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

    2012-12-15

    The aldol reaction is one of the most powerful and versatile methods for the construction of C-C bonds. Traditionally, this reaction was developed in a stoichiometric version; however, great efforts in the development of chiral catalysts for aldol reactions were performed in recent years. Thus, in this review article, the development of metal-mediated chiral catalysts in Mukaiyama-type aldol reaction, reductive aldol reaction and direct aldol reaction are discussed. Moreover, the application of these catalysts in the total synthesis of complex molecules is discussed. (author)

  10. Enantioselective syntheses of aeruginosin 298-A and its analogues using a catalytic asymmetric phase-transfer reaction and epoxidation.

    Science.gov (United States)

    Ohshima, Takashi; Gnanadesikan, Vijay; Shibuguchi, Tomoyuki; Fukuta, Yuhei; Nemoto, Tetsuhiro; Shibasaki, Masakatsu

    2003-09-17

    We developed a versatile synthetic process for aeruginosin 298-A as well as several attractive analogues, in which all stereocenters were controlled by a catalytic asymmetric phase-transfer reaction and epoxidation. Furthermore, drastic counteranion effects in phase-transfer catalysis were observed for the first time, making it possible to three-dimensionally fine-tune the catalyst (ketal part, aromatic part, and counteranion).

  11. Asymmetric Michael Addition Mediated by Chiral Ionic Liquids.

    Science.gov (United States)

    Suzuki, Yumiko

    2018-06-01

    Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines.

  12. Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

    Science.gov (United States)

    Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2010-04-07

    The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

  13. The asymmetric total synthesis of (+)- and (-)-trypargine via Noyori asymmetric transfer hydrogenation

    International Nuclear Information System (INIS)

    Pilli, Ronaldo A.; Rodrigues Junior, Manoel Trindade

    2009-01-01

    A concise and efficient total synthesis of (+)- and (-)-trypargine (6 steps and 38% overall yield), a 1-substituted β-carboline guanidine alkaloid isolated from the skin of the African frog K. senegalensis, was developed based on the construction of the b-carboline moiety via Bischler-Napieralski reaction and the enantioselective reduction of the dihydro-β-carboline intermediate via an asymmetric transfer hydrogenation reaction using Noyori's protocol. (author)

  14. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach

    Directory of Open Access Journals (Sweden)

    Pankaj Chauhan

    2012-12-01

    Full Text Available Ball-milling and pestle and mortar grinding have emerged as powerful methods for the development of environmentally benign chemical transformations. Recently, the use of these mechanochemical techniques in asymmetric organocatalysis has increased. This review highlights the progress in asymmetric organocatalytic reactions assisted by mechanochemical techniques.

  15. Asymmetric Michael Addition Mediated by Chiral Ionic Liquids

    Science.gov (United States)

    Suzuki, Yumiko

    2018-01-01

    Chiral ionic liquids with a focus on their applications in asymmetric Michael additions and related reactions were reviewed. The examples were classified on the basis of the mode of asymmetric induction (e.g., external induction/non-covalent interaction or internal induction/covalent bond formation), the roles in reactions (as a solvent or catalyst), and their structural features (e.g., imidazolium-based chiral cations, other chiral oniums; proline derivatives). Most of the reactions with high chiral induction are Michael addition of ketones or aldehydes to chalcones or nitrostyrenes where proline-derived chiral ionic liquids catalyze the reaction through enamine/ iminium formation. Many reports demonstrate the recyclability of ionic liquid-tagged pyrrolidines. PMID:29861702

  16. Síndrome de Horner y bloqueo del plexo braquial ipsilateral en un caso de analgesia epidural para el trabajo del parto Horner´s sydrome and ipsilateral brachial plexus block during an epidural analgesia labour procedure

    OpenAIRE

    J. Avellanosa; J. Vera; P. Morillas; E. Gredilla; F. Gilsanz

    2006-01-01

    El Síndrome de Horner es una complicación de la anestesia epidural que aparece más frecuentemente en pacientes obstétricas debido a los cambios fisiológicos y anatómicos propios del embarazo; sin embargo, su incidencia es baja, y sólo se han descrito dos casos previos asociando un bloqueo del plexo braquial. Presentamos el caso de una gestante de 23 años que precisó analgesia epidural para el trabajo de parto. Tras comprobar la correcta colocación del catéter se administró una dosis inicial e...

  17. The asymmetric reactions of mean and volatility of stock returns to domestic and international information based on a four-regime double-threshold GARCH model

    Science.gov (United States)

    Chen, Cathy W. S.; Yang, Ming Jing; Gerlach, Richard; Jim Lo, H.

    2006-07-01

    In this paper, we investigate the asymmetric reactions of mean and volatility of stock returns in five major markets to their own local news and the US information via linear and nonlinear models. We introduce a four-regime Double-Threshold GARCH (DTGARCH) model, which allows asymmetry in both the conditional mean and variance equations simultaneously by employing two threshold variables, to analyze the stock markets’ reactions to different types of information (good/bad news) generated from the domestic markets and the US stock market. By applying the four-regime DTGARCH model, this study finds that the interaction between the information of domestic and US stock markets leads to the asymmetric reactions of stock returns and their variability. In addition, this research also finds that the positive autocorrelation reported in the previous studies of financial markets may in fact be mis-specified, and actually due to the local market's positive response to the US stock market.

  18. Tourist Demand Reactions: Symmetric or Asymmetric across the Business Cycle?

    Science.gov (United States)

    Bronner, Fred; de Hoog, Robert

    2017-09-01

    Economizing and spending priorities on different types of vacations are investigated during two periods: an economic downturn and returning prosperity. Two nation-wide samples of vacationers are used: one during a downturn, the other one at the start of the recovery period. Through comparing the results, conclusions can be drawn about symmetric or asymmetric tourist demand across the business cycle. The main summer holiday has an asymmetric profile: being fairly crisis-resistant during a recession and showing considerable growth during an expansion. This does not apply to short vacations and day trips, each having a symmetric profile: during a recession they experience substantial reductions and during expansion comparable growth. So when talking about tourist demand in general , one cannot say that it is symmetric or asymmetric across the business cycle: it depends on the type of vacation. Differences in tourist demand are best explained by the role of Quality-of-Life for vacationers.

  19. Asymmetric Baylis-Hillman Reaction between Chiral Activated Alkenes and Aromatic Aldehydes in Me3N/H2O/Solvent Medium

    Institute of Scientific and Technical Information of China (English)

    Ke HE; Zheng Hong ZHOU; Hong Ying TANG; Guo Feng ZHAO; Chu Chi TANG

    2005-01-01

    Chiral activated alkene, L-menthyl acrylate and (+)-N-α-phenylethyl acrylamide,induced asymmetric Baylis-Hillman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous medium. The corresponding Baylis-Hillman adducts were obtained in good chemical yield with moderate to excellent diastereoselectivity (up to 99% de).

  20. [What would you do in front of a patient with a Horner syndrome?

    Science.gov (United States)

    Camós-Carreras, A; Fontana, S; Ortiz-Pérez, S

    2018-03-01

    Horner's syndrome (HS) occurs when there is disruption to the oculosympathetic pathway. Its features include eyelid ptosis, miosis and anhidrosis. The aetiology of this syndrome is varied and includes tumours, trauma, vascular disease and iatrogenic. Different pharmacologic tests are used for diagnosis, such as cocaine, hydroxyamphetamine and apraclonidine; while neuroimaging helps elucidating the aetiology. We present a case of a 63-year-old female referred to our service with a 4-month history of right eyelid ptosis. During examination right miosis was noted. The patient reported a history of multinodular goiter. Pharmacologic tests and neuroimaging confirmed the diagnosis of HS secondary to thyroid disease. Copyright © 2016 Sociedad Española de Médicos de Atención Primaria (SEMERGEN). Publicado por Elsevier España, S.L.U. All rights reserved.

  1. Bifunctional nanocrystalline MgO for chiral epoxy ketones via Claisen-Schmidt condensation-asymmetric epoxidation reactions.

    Science.gov (United States)

    Choudary, Boyapati M; Kantam, Mannepalli L; Ranganath, Kalluri V S; Mahendar, Koosam; Sreedhar, Bojja

    2004-03-24

    Design and development of a truly nanobifunctional heterogeneous catalyst for the Claisen-Schmidt condensation (CSC) of benzaldehydes with acetophenones to yield chalcones quantitatively followed by asymmetric epoxidation (AE) to afford chiral epoxy ketones with moderate to good yields and impressive ee's is described. The nanomagnesium oxide (aerogel prepared) NAP-MgO was found to be superior over the NA-MgO and CM-MgO in terms of activity and enantioselectivity as applicable in these reactions. An elegant strategy for heterogenization of homogeneous catalysts is presented here to evolve single-site chiral catalysts for AE by a successful transfer of molecular chemistry to surface metal-organic chemistry with the retention of activity, selectivity/enantioselectivity. Brønsted hydroxyls are established as sole contributors for the epoxidation reaction, while they add on to the CSC, which is largely driven by Lewis basic O2-sites. Strong hydrogen-bond interactions between the surface -OH on MgO and -OH groups of diethyl tartrate are found inducing enantioselectivity in the AE reaction. Thus, the nanocrystalline NAP-MgO with its defined shape, size, and accessible OH groups allows the chemisorption of TBHP, DET, and olefin on its surface to accomplish single-site chiral catalysts to provide optimum ee's in AE reactions.

  2. Recent Advances in Substrate-Controlled Asymmetric Cyclization for Natural Product Synthesis

    Directory of Open Access Journals (Sweden)

    Jeyun Jo

    2017-06-01

    Full Text Available Asymmetric synthesis of naturally occurring diverse ring systems is an ongoing and challenging research topic. A large variety of remarkable reactions utilizing chiral substrates, auxiliaries, reagents, and catalysts have been intensively investigated. This review specifically describes recent advances in successful asymmetric cyclization reactions to generate cyclic architectures of various natural products in a substrate-controlled manner.

  3. T1-nerve root neuroma presenting with apical mass and Horner's syndrome

    Directory of Open Access Journals (Sweden)

    Podnar Simon

    2007-03-01

    Full Text Available Abstract Background The appearance of dumbbell neuroma of the first thoracic root is extremely rare. The extradural component of a T1-dumbbell neuroma may present as an apical mass. The diagnosis of hand weakness is complex and may be delayed in T1-neuroma because of absence of the palpable cervical mass. One-stage removal of a T1-root neuroma and its intrathoracic extension demanded an extended posterior midline approach in the sitting position. Case presentation A 51-year old man had suffered a traumatic partial tendon rupture of his wrist flexor muscles 6 years ago. Since the incident he occasionally felt fullness and tenderness in the affected forearm with some tingling in his fingers bilaterally. During the last two years the hand weakness was continuous and hypotrophy of the medial flexor and intrinsic hand muscles had become apparent. Electrophysiological studies revealed an ulnar neuropathy in addition to mild median and radial nerve dysfunction, including a mild contralateral carpal tunnel syndrome. The diagnostic work-up for multiple mononeuropathy in the upper extremity was negative. Repeated electrophysiological studies revealed fibrillations in the C7 paravertebral muscles on the affected side. Chest x-ray revealed a large round apical mass on the affected side. A Horner's syndrome was noted at this point of diagnostic work-up. MRI of the cervical and thoracic spine revealed a dumbbell T1 neuroma enlarging the intervertebral foramen at T1-2 and a 5 cm large extradural tumor with extension into the apex of the ipsilateral lung. The patient underwent surgery in sitting position using a left dorsal midline approach. Although the T1 root could not be preserved, the patient's neurological condition was unchanged after the surgery. Conclusion Extended posterior midline exposure described here using hemilaminectomy, unilateral facetectomy and costo-transversectomy is efficient and safe for one-stage removal of dumbbell tumors at the T1

  4. DETERMINING SOIL REACTIONS AND THE VALUE OF DEVIATION FROM A LINEAR TRAJECTORY OF ASYMMETRICAL SOIL THRUST WORKING BODY

    Directory of Open Access Journals (Sweden)

    S. Kravets

    2017-12-01

    Full Text Available The construction of underground communications in urban conditions is very difficult due to the large number of existing communications. Thus, it is necessary to change the trajectory of the horizontal well during soil thrust boring. An analytical method for determining soil reactions and the deviation of the trajectory of an asymmetric soil thrust working body, which can be used to correct or control the trajectory during puncture, is suggested.

  5. Asymmetric catalysis in the cyclopropanation of olefins; Catalise assimetrica na ciclopropanacao de olefinas

    Energy Technology Data Exchange (ETDEWEB)

    Leao, Raquel A.C.; Ferreira, Vitor F.; Pinheiro, Sergio [Universidade Federal Fluminense (UFF), Niteroi, RJ (Brazil). Dept. de Quimica Organica]. E-mail: cegvito@vm.uff.br

    2007-07-01

    The main methodologies in the asymmetric cyclopropanation of alkenes with emphasis on asymmetric catalysis are covered. Examples are the Simmons-Smith reaction, the use of diazoalkanes and reactions carried out by decomposition of alpha-diazoesters in the presence of transition metals. (author)

  6. Stereoselectivity in ene reactions with 1O2: matrix effects in polymer supports, photo-oxygenation of organic salts and asymmetric synthesis.

    Science.gov (United States)

    Griesbeck, Axel G; Bartoschek, Anna; Neudörfl, Jörg; Miara, Claus

    2006-01-01

    The ene reaction of chiral allylic alcohols is applied as a tool for the investigation of intrapolymer effects by means of the stereoselectivity of the singlet-oxygen addition. The diastereo selectivity strongly depends on the structure of the polymer, the substrate loading degree and also on the degree of conversion demonstrating additional supramolecular effects evolving during the reaction. The efficiency and the stability of polymer-bound sensitizers were evaluated by the ene reaction of singlet oxygen with citronellol. The ene reaction with chiral ammonium salts of tiglic acid was conducted under solution phase conditions or in polystyrene beads under chiral contact ion-pair conditions. The products thus obtained precipitate during the photoreaction as ammonium salts. Moderate asymmetric induction was observed for this procedure for the first time.

  7. Polystyrene copolymer supported by substituted (1R,2R)-1,2-diphenylethane-1,2-diamine-copper(II) complexes: a recyclable catalyst for asymmetric Henry reactions

    Czech Academy of Sciences Publication Activity Database

    Androvič, L.; Drabina, P.; Panov, I.; Frumarová, Božena; Kalendová, A.; Sedlák, M.

    2014-01-01

    Roč. 25, č. 9 (2014), s. 775-780 ISSN 0957-4166 Institutional support: RVO:61389013 Keywords : cooper complexes * copolymers * asymmetric Henry reaction Subject RIV: CC - Organic Chemistry Impact factor: 2.155, year: 2014

  8. Asymmetric Strecker Synthesis of α-Amino Acids via a Crystallization-Induced Asymmetric Transformation Using (R)-Phenylglycine Amide as Chiral Auxiliary

    NARCIS (Netherlands)

    Boesten, Wilhelmus H.J.; Seerden, Jean-Paul G.; Lange, Ben de; Dielemans, Hubertus J.A.; Elsenberg, Henk L.M.; Kaptein, Bernard; Moody, Harold M.; Kellogg, Richard M.; Broxterman, Quirinus B.

    2001-01-01

    Diastereoselective Strecker reactions based on (R)-phenylglycine amide as chiral auxiliary are reported. The Strecker reaction is accompanied by an in situ crystallization-induced asymmetric transformation, whereby one diastereomer selectively precipitates and can be isolated in 76-93% yield and dr

  9. alpha,beta-unsaturated 2-acyl imidazoles as a practical class of dienophiles for the DNA-Based catalytic asymmetric diels-alder reaction in water

    NARCIS (Netherlands)

    Boersma, A.J.; Feringa, B.L.; Roelfes, G.

    2007-01-01

    alpha,beta-Unsaturated 2-acyl imidazoles are a novel and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in water. The Diels-Alder products are obtained with very high diastereoselectivities and enantioselectivities in the range of 83-98%. The catalytic

  10. Syntheses of the hexahydroindene cores of indanomycin and stawamycin by combinations of iridium-catalyzed asymmetric allylic alkylations and intramolecular Diels-Alder reactions.

    Science.gov (United States)

    Gärtner, Martin; Satyanarayana, Gedu; Förster, Sebastian; Helmchen, Günter

    2013-01-02

    Short and concise syntheses of the hexahydroindene cores of the antibiotics indanomycin (X-14547 A) and stawamycin are presented. Key methods used are an asymmetric iridium-catalyzed allylic alkylation, a modified Julia olefination, a Suzuki-Miyaura coupling, and an intramolecular Diels-Alder reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Asymmetric Synthesis of P-Chiral Diphosphines. Steric Effects on the Palladium-Complex-Promoted Asymmetric Diels-Alder Reaction between a Dimethylphenylphosphole and (E/Z)-Methyl-Substituted Diphenylvinylphosphines.

    Science.gov (United States)

    Aw, Beng-Hwee; Hor, T. S. Andy; Selvaratnam, S.; Mok, K. F.; White, Andrew J. P.; Williams, David J.; Rees, Nicholas H.; McFarlane, William; Leung, Pak-Hing

    1997-05-07

    The organopalladium complex containing ortho-metalated (S)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary has been used successfully to promote the asymmetric [4+2] Diels-Alder reactions between 1-phenyl-3,4-dimethylphosphole and the following coordinated dienophiles: (a) diphenylvinylphosphine; (b) (E)-diphenyl-1-propenylphosphine; (c) (Z)-diphenyl-1-propenylphosphine. Reaction a generates three carbon and one phosphorus stereogenic centers while reactions b and c each produce four carbon and one phosphorus chiral centers. In dichloromethane, all three reactions proceeded smoothly at room temperature giving the corresponding rigid diphosphines in high yields. Under similar reaction conditions, the reaction times observed for reactions a-c are 2, 3, and 50 h, respectively. Two-dimensional ROESY NMR studies confirmed that the prolonged reaction time required for reaction c is due to several major repulsive interactions between the chiral naphthylamine auxiliary and the (Z)-methyl-substituted vinylphosphine in the transition state. Nevertheless, all three reactions gave the corresponding rigid diphosphine in high yields. The absolute stereochemistries of the three bidentate phosphine ligands that were produced from the cycloaddition reactions have been assigned by 2D ROESY NMR spectroscopy. These diphosphines are powerful sequesterers of group 8 metals although they are highly air-sensitive in the free ligand form. The coordination chemistry and the absolute stereochemistry of the optically active complex [1alpha,4alpha,5alpha(S),6alpha(S),7R]-dichloro[5-(diphenylphosphino)-2,3,6-trimethy-7-phenyl-7-phosphabicyclo[2.2.1]-hept-2-ene-P(5)(),P(7)()]palladium(II) has been studied by single-crystal X-ray analysis. Crystal structure data: C(27)H(28)Cl(2)P(2)Pd, M(r) = 591.7; triclinic; space group P1; a = 8.643(3), b = 9.044(6), c = 9.058(4) Å; alpha = 102.75(4) degrees, beta = 108.59(2) degrees, gamma = 97.82(3) degrees; V = 638.0(5) Å(3); Z = 1; R(1) = 0.036.

  12. Asymmetric Total Synthesis of Ieodomycin B

    Directory of Open Access Journals (Sweden)

    Shuangjie Lin

    2017-01-01

    Full Text Available Ieodomycin B, which shows in vitro antimicrobial activity, was isolated from a marine Bacillus species. A novel asymmetric total synthetic approach to ieodomycin B using commercially available geraniol was achieved. The approach involves the generation of 1,3-trans-dihydroxyl at C-3 and C-5 positions via a Crimmins-modified Evans aldol reaction and a chelation-controlled Mukaiyama aldol reaction of a p-methoxybenzyl-protected aldehyde, as well as the generation of a lactone ring in a deprotection–lactonization one-pot reaction.

  13. Chiral ferrocenes in asymmetric catalysis: synthesis and applications

    National Research Council Canada - National Science Library

    Dai, Li-Xin; Hou, Xue-Long

    2010-01-01

    .... It provides a thorough overview of the synthesis and characterization of different types of chiral ferrocene ligands, their application to various catalytic asymmetric reactions, and versatile chiral...

  14. A high-performance liquid chromatography-electronic circular dichroism online method for assessing the absolute enantiomeric excess and conversion ratio of asymmetric reactions

    Science.gov (United States)

    Zhang, Xiang; Wang, Mingchao; Li, Li; Yin, Dali

    2017-03-01

    Asymmetric reactions often need to be evaluated during the synthesis of chiral compounds. However, traditional evaluation methods require the isolation of the individual enantiomer, which is tedious and time-consuming. Thus, it is desirable to develop simple, practical online detection methods. We developed a method based on high-performance liquid chromatography-electronic circular dichroism (HPLC-ECD) that simultaneously analyzes the material conversion ratio and absolute optical purity of each enantiomer. In particular, only a reverse-phase C18 column instead of a chiral column is required in our method because the ECD measurement provides a g-factor that describes the ratio of each enantiomer in the mixtures. We used our method to analyze the asymmetric hydrosilylation of β-enamino esters, and we discussed the advantage, feasibility, and effectiveness of this new methodology.

  15. Vortex Dynamics of Asymmetric Heave Plates

    Science.gov (United States)

    Rusch, Curtis; Maurer, Benjamin; Polagye, Brian

    2017-11-01

    Heave plates can be used to provide reaction forces for wave energy converters, which harness the power in ocean surface waves to produce electricity. Heave plate inertia includes both the static mass of the heave plate, as well as the ``added mass'' of surrounding water accelerated with the object. Heave plate geometries may be symmetric or asymmetric, with interest in asymmetric designs driven by the resulting hydrodynamic asymmetry. Limited flow visualization has been previously conducted on symmetric heave plates, but flow visualization of asymmetric designs is needed to understand the origin of observed hydrodynamic asymmetries and their dependence on the Keulegan-Carpenter number. For example, it is hypothesized that the time-varying added mass of asymmetric heave plates is caused by vortex shedding, which is related to oscillation amplitude. Here, using direct flow visualization, we explore the relationship between vortex dynamics and time-varying added mass and drag. These results suggest potential pathways for more advanced heave plate designs that can exploit vortex formation and shedding to achieve more favorable hydrodynamic properties for wave energy converters.

  16. Asymmetric Diels-Alder Reaction of α,β-Unsaturated Oxazolidin-2-one Derivatives Catalyzed by a Chiral Fe(III)-Bipyridine Diol Complex.

    Science.gov (United States)

    Li, Mao; Carreras, Virginie; Jalba, Angela; Ollevier, Thierry

    2018-02-16

    An asymmetric Fe III -bipyridine diol catalyzed Diels-Alder reaction of α,β-unsaturated oxazolidin-2-ones has been developed. Among various Fe II /Fe III salts, Fe(ClO 4 ) 3 ·6H 2 O was selected as the Lewis acid of choice. The use of a low catalyst loading (2 mol % of Fe(ClO 4 ) 3 ·6H 2 O and 2.4 mol % of Bolm's ligand) afforded high yields (up to 99%) and high enantiomeric excesses (up to 98%) of endo-cycloadducts for the Diels-Alder reaction between cyclopentadiene and substituted acryloyloxazolidin-2-ones. Other noncyclic dienes led to decreased enantioselectivities. A proposed model supports the observed stereoinduction.

  17. Catalytic asymmetric synthesis of the alkaloid (+)-myrtine

    NARCIS (Netherlands)

    Pizzuti, Maria Gabriefla; Minnaard, Adriaan J.; Feringa, Ben L.

    2008-01-01

    A new protocol for the asymmetric synthesis of trans-2,6-disubstituted-4-piperidones has been developed using a catalytic enantioselective conjugate addition reaction in combination with a diastereoselective lithiation-substitution sequence; an efficient synthesis of (+)-myrtine has been achieved

  18. Asymmetric Organocatalytic Cycloadditions

    DEFF Research Database (Denmark)

    Mose, Rasmus

    2016-01-01

    has gained broad recognition as it has found several applications in academia and industry. The [4+2] cycloaddition has also been performed in an enantioselective aminocatalytic fashion which allows the generation of optically active products. In this thesis it is demonstrated how trienamines can......Since the onset of the new millennium the field of organocatalysis has undergone a great expansion led by investigations in the field of aminocatalysis. This thesis will address some recent developments in aminocatalyzed cycloadditions and provide a theoretical background hereto. Cycloadditions...... undergo cascade reactions with different electron deficient dienophiles in Diels Alder – nucleophilic ring closing reactions. This methodology opens up for the direct asymmetric formation of hydroisochromenes and hydroisoquinolines which may possess interesting biological activities. It is also...

  19. Catálise assimétrica na ciclopropanação de olefinas Asymmetric catalysis in the cyclopropanation of olefins

    Directory of Open Access Journals (Sweden)

    Raquel A. C. Leão

    2007-01-01

    Full Text Available The main methodologies in the asymmetric cyclopropanation of alkenes with emphasis on asymmetric catalysis are covered. Exemples are the Simmons-Smith reaction, the use of diazoalkanes and reactions carried out by decomposition of alpha-diazoesters in the presence of transition metals.

  20. Copper(I)-Catalyzed Asymmetric Desymmetrization through Inverse-Electron-Demand aza-Diels-Alder Reaction: Efficient Access to Tetrahydropyridazines Bearing a Unique α-Chiral Silane Moiety.

    Science.gov (United States)

    Wei, Liang; Zhou, Yu; Song, Zhi-Min; Tao, Hai-Yan; Lin, Zhenyang; Wang, Chun-Jiang

    2017-04-11

    An unprecedented copper(I)-catalyzed asymmetric desymmetrization of 5-silylcyclopentadienes with in situ formed azoalkene was realized through an inverse-electron-demand aza-Diels-Alder reaction (IEDDA) pathway, in which 5-silylcyclopentadienes served as efficient enophiles. This new protocol provides a facile access to the biologically important heterocyclic tetrahydropyridazines containing a unique α-chiral silane motif and three adjoining stereogenic centers in generally good yield (up to 92 %) with exclusive regioselectivity, high diastereoselectivity (>20:1 diastereomeric ratio), and excellent enantioselectivity (up to 98 % enantiomeric excess). DFT calculations and control experiments further confirmed the proposed reaction mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Tendinitis retrofaríngea, plexopatía braquial y síndrome de Horner como consecuencia de una postura cervical anómala

    OpenAIRE

    Benito Orejas, José Ignacio; Torres Morientes, Luis M.; Fernández Buey, Nieves; Rodríguez Velasco, Margarita; Morais Pérez, Darío

    2014-01-01

    [ES] Introducción y objetivo: Presentamos el caso clínico de un paciente que, a consecuencia de una mala postura cervical, manifiesta una sintomatología y exploración compatibles con tendinitis retrofaríngea, síndrome de Horner y plexopatía braquial del mismo lado. No habiendo encontrado en la literatura una descripción similar, analizamos las características y posible fisiopatología de esta rara asociación. Caso clínico: Tras consumir en exceso alcohol y drogas, un hombre joven se queda dorm...

  2. New chiral ligands in asymmetric catalysis. Application in stabilization of metal nanoparticles

    OpenAIRE

    Axet Martí, M. Rosa

    2006-01-01

    Thesis M. Rosa AxetThis thesis deals with the development and application of diphosphite ligands derived from carbohydrates to rhodium-catalysed asymmetric hydroformylation and hydrogenation reactions. The use of various carbohydrate derivative ligands as stabilisers of metal nanoparticles is also studied. The synthesis and the characterisation of the series of diphosphite ligands are described in Chapter 2. The results of the asymmetric hydroformylation of styrene and related vinyl arenes ar...

  3. A Reply to the Commentaries on "School-wide PBIS: An Example of Applied Behavior Analysis Implemented at a Scale of Social Importance" by Horner and Sugai (2015): PBIS is Function over Form: The Clear Behavioral Roots and Opportunities the PBIS Framework presents to the Field of Behavior Analysis Moving Forward.

    Science.gov (United States)

    Putnam, Robert F; Knoster, Tim

    2016-03-01

    In the previous issue of Behavior Analysis in Practice (May 2015), a special section of the journal was devoted to positive behavior intervention and support (PBIS). Horner and Sugai (2015) published a manuscript providing an overview of school-wide PBIS describing how PBIS is an example of applied behavior analysis at a scale of social importance. A number of manuscripts providing commentary on the Horner and Sugai manuscript were also published in this special section of the journal. This paper will review this PBIS manuscript along with the associated commentaries published in the May 2015 special section.

  4. Asymmetric synthesis of synthetic alkaloids by a tandem biocatalysis/Ugi/Pictet-Spengler-type

    NARCIS (Netherlands)

    Znabet, A.; Zonneveld, J.; Janssen, E.; de Kanter, F.J.J.; Helliwell, M.; Turner, N.J.; Ruijter, E.; Orru, R.V.A.

    2010-01-01

    We have combined the biocatalytic desymmetrization of 3,4-cis-substituted meso-pyrrolidines with an Ugi-type multicomponent reaction followed in situ by a Pictet-Spengler-type cyclization reaction sequence for the rapid asymmetric synthesis of alkaloid-like polycyclic compounds. © The Royal Society

  5. Novel phosphonium salts and bifunctional organocatalysts in asymmetric synthesis

    OpenAIRE

    Moore, Graham

    2013-01-01

    This thesis details the syntheses of catalysts and their applications in asymmetric reactions. Initially, the project focused on phase transfer catalysts; quaternary phosphonium salts derived from diethyl tartrate or from commercially available phosphorus compounds and their use primarily in the alkylation of N,N-diphenyl methylene glycine tert-butyl ester. Although some of the salts showed the ability to catalyse the alkylation reaction, all products obtained were racemic. The project then f...

  6. Asymmetric Diels-Alder Reaction of α-Substituted and β,β-Disubstituted α,β-Enals via Diarylprolinol Silyl Ether for the Construction of All-Carbon Quaternary Stereocenters.

    Science.gov (United States)

    Hayashi, Yujiro; Bondzic, Bojan P; Yamazaki, Tatsuya; Gupta, Yogesh; Ogasawara, Shin; Taniguchi, Tohru; Monde, Kenji

    2016-10-24

    The asymmetric Diels-Alder reaction of α-substituted acrolein proceeds in the presence of the trifluoroacetic acid salt of trifluoromethyl-substituted diarylprolinol silyl ether to afford the exo-isomer with both excellent diastereoselectivity and high enantioselectivity. In the Diels-Alder reaction of a β,β-disubstituted α,β-unsaturated aldehyde, good exo-selectivity and excellent enantioselectivity was obtained when the perchloric acid salt of the bulky triisopropyl silyl ether of trifluoromethyl substituted diarylprolinol was employed as an organocatalyst in the presence of water. In both cases, all-carbon quaternary stereocenters are constructed enantioselectively. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Updating the asymmetric osmium-catalyzed dihydroxylation (AD) mnemonic. Q2MM modeling and new kinetic measurements

    DEFF Research Database (Denmark)

    Fristrup, Peter; Tanner, David Ackland; Norrby, Per-Ola

    2003-01-01

    The mnemonic device for predicting stereoselectivities in the Sharpless asymmetric dihydroxylation (AD) reaction has been updated based on extensive computational studies. Kinetic measurements from competition reactions validate the new proposal. The interactions responsible for the high stereose...

  8. Automated Quantum Mechanical Predictions of Enantioselectivity in a Rhodium-Catalyzed Asymmetric Hydrogenation.

    Science.gov (United States)

    Guan, Yanfei; Wheeler, Steven E

    2017-07-24

    A computational toolkit (AARON: An automated reaction optimizer for new catalysts) is described that automates the density functional theory (DFT) based screening of chiral ligands for transition-metal-catalyzed reactions with well-defined reaction mechanisms but multiple stereocontrolling transition states. This is demonstrated for the Rh-catalyzed asymmetric hydrogenation of (E)-β-aryl-N-acetyl enamides, for which a new C 2 -symmetric phosphorus ligand is designed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Non-Classical C–H···X Hydrogen Bonding and Its Role in Asymmetric Organocatalysis

    KAUST Repository

    Ajitha, Manjaly John

    2016-08-17

    Non-classical hydrogen bonds (NCHBs) have attracted significant interest in the past decade particularly because of their important role in asymmetric catalytic systems. These weak interactions (< 4 kcal/mol) offer much flexibility in the preorganization of molecular entities required to achieve high enantioselectivity. Herein, we review some recent important organocatalytic asymmetric reactions where a NCHB serves as a critical factor in determining the stereoselectivity.

  10. The Chiral Pool in the Pictet–Spengler Reaction for the Synthesis of β-Carbolines

    Directory of Open Access Journals (Sweden)

    Renato Dalpozzo

    2016-05-01

    Full Text Available The Pictet–Spengler reaction (PSR is the reaction of a β-arylethylamine with an aldehyde or ketone, followed by ring closure to give an aza-heterocycle. When the β-arylethylamine is tryptamine, the product is a β-carboline, a widespread skeleton in natural alkaloids. In the natural occurrence, these compounds are generally enantiopure, thus the asymmetric synthesis of these compounds have been attracting the interest of organic chemists. This review aims to give an overview of the asymmetric PSR, in which the chirality arises from optically pure amines or carbonyl compounds both from natural sources and from asymmetric syntheses to assemble the reaction partners.

  11. A concise summary of experimental facts about the Soai reaction.

    Science.gov (United States)

    Gehring, Timo; Busch, Mark; Schlageter, Martin; Weingand, Daniel

    2010-01-01

    The Soai reaction amplifies small enantiomeric excesses in a spectacular manner. Being known for 20 years, it has drawn the attention of many scientists in different fields as it is to date the only chemical reaction offering the chance to study the phenomenon of asymmetric autocatalysis in conjunction with high amplification of enantiomeric excess (ee). This mini-review comprises an introduction to the discovery of asymmetric autocatalysis with amplification of ee and a concise summary of published experimental results showing which starting materials and reaction parameters play an important role in this reaction and which influences are understood. It is addressed especially to scientists entering the field of the Soai reaction to get a quick overview of important aspects. © 2010 Wiley-Liss, Inc.

  12. Chemical reaction due to stronger Ramachandran interaction

    Indian Academy of Sciences (India)

    actions between two polarized atoms are responsible for initiating a chemical reaction, either before or after ... Chemical reaction; Ramachandran interaction; anisotropic and asymmetric polarization; ionization ..... man sequence exactly, including the generalized mech- ..... We now move on and rearrange Eq. (8) to arrive at.

  13. Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

    OpenAIRE

    Worawan Bhanthumnavin; Tirayut Vilaivan

    2010-01-01

    Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects ...

  14. Catalytic asymmetric epoxidation of alpha,beta-unsaturated amides: efficient synthesis of beta-aryl alpha-hydroxy amides using a one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process.

    Science.gov (United States)

    Nemoto, Tetsuhiro; Kakei, Hiroyuki; Gnanadesikan, Vijay; Tosaki, Shin-Ya; Ohshima, Takashi; Shibasaki, Masakatsu

    2002-12-11

    The catalytic asymmetric epoxidation of alpha,beta-unsaturated amides using Sm-BINOL-Ph3As=O complex was succeeded. Using 5-10 mol % of the asymmetric catalyst, a variety of amides were epoxidized efficiently, yielding the corresponding alpha,beta-epoxy amides in up to 99% yield and in more than 99% ee. Moreover, the novel one-pot tandem process, one-pot tandem catalytic asymmetric epoxidation-Pd-catalyzed epoxide opening process, was developed. This method was successfully utilized for the efficient synthesis of beta-aryl alpha-hydroxy amides, including beta-aryllactyl-leucine methyl esters. Interestingly, it was found that beneficial modifications on the Pd catalyst were achieved by the constituents of the first epoxidation, producing a more suitable catalyst for the Pd-catalyzed epoxide opening reaction in terms of chemoselectivity.

  15. [Reaction mechanism studies of heavy ion induced nuclear reactions]: Annual progress report, October 1987

    International Nuclear Information System (INIS)

    Mignerey, A.C.

    1987-10-01

    The experiments which this group has been working on seek to define the reaction mechanisms responsible for complex fragment emission in heavy ion reactions. The reactions studied are La + La, La + Al, and La + Cu at 46.8 MeV/u; and Ne + Ag and Ne + Au reactions at 250 MeV/u. Another experimental program at the Oak Ridge Hollifield Heavy Ion Research Facility (HHIRF) is designed to measure the excitation energy division between reaction products in asymmetric deep inelastic reactions. A brief description is given of progress to date, the scientific goals of this experiment and the plastic phoswich detectors developed for this experiment

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

    Directory of Open Access Journals (Sweden)

    Erli Sugiono

    2013-11-01

    Full Text Available 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.

  17. All Pseudocapacitive MXene-RuO2 Asymmetric Supercapacitors

    KAUST Repository

    Jiang, Qiu

    2018-01-23

    2D transition metal carbides and nitrides, known as MXenes, are an emerging class of 2D materials with a wide spectrum of potential applications, in particular in electrochemical energy storage. The hydrophilicity of MXenes combined with their metallic conductivity and surface redox reactions is the key for high-rate pseudocapacitive energy storage in MXene electrodes. However, symmetric MXene supercapacitors have a limited voltage window of around 0.6 V due to possible oxidation at high anodic potentials. In this study, the fact that titanium carbide MXene (Ti3C2Tx) can operate at negative potentials in acidic electrolyte is exploited, to design an all-pseudocapacitive asymmetric device by combining it with a ruthenium oxide (RuO2) positive electrode. This asymmetric device operates at a voltage window of 1.5 V, which is about two times wider than the operating voltage window of symmetric MXene supercapacitors, and is the widest voltage window reported to date for MXene-based supercapacitors. The complementary working potential windows of MXene and RuO2, along with proton-induced pseudocapacitance, significantly enhance the device performance. As a result, the asymmetric devices can deliver an energy density of 37 µW h cm−2 at a power density of 40 mW cm−2, with 86% capacitance retention after 20 000 charge–discharge cycles. These results show that pseudocapacitive negative MXene electrodes can potentially replace carbon-based materials in asymmetric electrochemical capacitors, leading to an increased energy density.

  18. Multiple Hydrogen-Bond Activation in Asymmetric Brønsted Acid Catalysis

    KAUST Repository

    Liao, Hsuan-Hung

    2018-05-03

    An efficient protocol for the asymmetric synthesis of chiral tetrahydroquinolines bearing multiple stereogenic centers by means of asymmetric Brønsted acid catalysis was developed. A chiral 1,1′‐spirobiindane‐7,7′‐diol (SPINOL)‐based N‐triflylphosphoramide (NTPA) proved to be an effective Brønsted acid catalyst for the in situ generation of aza‐ortho‐quinone methides (aza‐o‐QMs) and their subsequent cycloaddition reaction with unactivated alkenes to provide the products with excellent diastereo‐ and enantioselectivities. In addition, DFT calculations provided insight into the activation mode and nature of the interactions between the N‐triflylphosphoramide catalyst and the generated aza‐o‐QMs.

  19. Multiple Hydrogen-Bond Activation in Asymmetric Brønsted Acid Catalysis

    KAUST Repository

    Liao, Hsuan-Hung; Hsiao, Chien-Chi; Atodiresei, Iuliana; Rueping, Magnus

    2018-01-01

    An efficient protocol for the asymmetric synthesis of chiral tetrahydroquinolines bearing multiple stereogenic centers by means of asymmetric Brønsted acid catalysis was developed. A chiral 1,1′‐spirobiindane‐7,7′‐diol (SPINOL)‐based N‐triflylphosphoramide (NTPA) proved to be an effective Brønsted acid catalyst for the in situ generation of aza‐ortho‐quinone methides (aza‐o‐QMs) and their subsequent cycloaddition reaction with unactivated alkenes to provide the products with excellent diastereo‐ and enantioselectivities. In addition, DFT calculations provided insight into the activation mode and nature of the interactions between the N‐triflylphosphoramide catalyst and the generated aza‐o‐QMs.

  20. Organocatalytic Hydrophosphonylation Reaction of Carbonyl Groups.

    Science.gov (United States)

    Herrera, Raquel P

    2017-09-01

    This revision is covering the limited examples reported for a pivotal strategy in the formation of C-P bonds such as the asymmetric organocatalytic hydrophosphonylation of carbonyl groups (Pudovik reaction). The scope and limitations, and the proposed mechanisms for the scarce different possibilities of asymmetric induction are also shown. The recent evolution and future trends of this undeveloped approach are commented. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Asymmetric Synthesis of Optically Active Spirocyclic Indoline Scaffolds through an Enantioselective Reduction of Indoles

    KAUST Repository

    Borrmann, Ruediger; Knop, Nils; Rueping, Magnus

    2016-01-01

    An enantioselective synthesis of spirocyclic indoline scaffolds was achieved by applying an asymmetric iridium-catalyzed hydrogenation of 3H-indoles. Low catalyst loadings and mild reaction conditions provide a broad range of differently substituted

  2. Ruthenacycles and Iridacycles as Catalysts for Asymmetric Transfer Hydrogenation and Racemisation

    NARCIS (Netherlands)

    Jerphagnon, Thomas; Haak, Robert; Berthiol, Florian; Gayet, Arnaud J.A.; Ritleng, Vincent; Holuigue, Alexandre; Pannetier, Nicolas; Pfeffer, Michel; Voelklin, Adeline; Lefort, Laurent; Verzijl, Gerard; Tarabiono, Chiara; Janssen, Dick B.; Minnaard, Adriaan J.; Feringa, Ben L.; Vries, Johannes G. de

    2010-01-01

    Ruthenacycles, which are easily prepared in a single step by reaction between enantiopure aromatic amines and [Ru(arene)Cl2]2 in the presence of NaOH and KPF6, are very good asymmetric transfer hydrogenation catalysts. A range of aromatic ketones were reduced using isopropanol in good yields with

  3. Evaluation of the Perceptual Characteristics of a Force Induced by Asymmetric Vibrations.

    Science.gov (United States)

    Tanabe, Takeshi; Yano, Hiroaki; Iwata, Hiroo

    2017-08-29

    This paper describes the properties of proprioceptive sensations induced by asymmetric vibration using a vibration speaker-type non-grounded haptic interface. We confirm that the vibration speaker generates a perceived force that pulls or pushes a user's hand in a particular direction when an asymmetric amplitude signal that is generated by inverting a part of a sine wave is input. In this paper, to verify the system with respect to various factors of force perception caused by asymmetric vibration, we conducted six experiments and the following results were obtained. (1) The force vector can be controlled by reversing the asymmetric waves. (2) By investigating the physical characteristics of the vibration, asymmetric vibration was confirmed. (3) The presentation of vibration in the shear direction on the finger pad is effective. (4) The point of subjective equality of the perceived force can be controlled by up to 0.43 N by changing the amplitude voltage of the input signals. (5) The minimum stimulation time required for force perception is 66.7 ms. (6) When the vibration is continuously presented for 40 to 50 s, the perceived force decreases because of adaptation. Hence, we confirmed that we can control both the direction and magnitude of the reaction force by changing the input signal of the vibration speaker.

  4. Solvent Effects in Asymmetric Hetero Diels-Alder and Ene Reactions

    DEFF Research Database (Denmark)

    Johannsen, Mogens; Jørgensen, Karl Anker

    1996-01-01

    The use of polar solvents such as nitromethane or 2-nitropropane leads to a significant improvement of the catalytic properties of a cationic copper-Lewis acid in the hetero Diels-Alder reaction of alkyl glyoxylates with dienes; The scope of a newly developed copper(II)-bisoxazoline catalyst...... for the hetero Diels-Alder reaction is demonstrated by the reaction of different dienes with alkyl glyoxylates in nitroalkane solvents with the formation of the hetero Diels-Alder adduct in high enantiomeric excess as the major product. The synthetic application of the reaction is exemplified by an improved...

  5. Discrete-Event Simulation with Agents for Modeling of Dynamic Asymmetric Threats in Maritime Security

    National Research Council Canada - National Science Library

    Ng, Chee W

    2007-01-01

    .... Discrete-event simulation (DES) was used to simulate a typical port-security, local, waterside-threat response model and to test the adaptive response of asymmetric threats in reaction to port-security procedures, while a multi-agent system (MAS...

  6. An Asymmetric Synthetic Approach to the A-ring of the Taxol Family of Anti-Cancer Compounds

    Directory of Open Access Journals (Sweden)

    M. L. Marin

    1998-02-01

    Full Text Available A synthetic route developed for the preparation of the A-ring of Taxol family of molecules is reported. By means of an intramolecular Diels-Alder reaction an asymmetric approach to this ring has been accomplished. Also, initial studies to prepare the A ring using an intramolecular Diels-Alder reaction have been successful.

  7. Lipase-catalyzed asymmetric synthesis of naphtho[2,3-c]furan-1(3H)-one derivatives by a one-pot dynamic kinetic resolution/intramolecular Diels-Alder reaction: Total synthesis of (-)-himbacine.

    Science.gov (United States)

    Sugiyama, Koji; Kawanishi, Shinji; Oki, Yasuhiro; Kamiya, Marin; Hanada, Ryosuke; Egi, Masahiro; Akai, Shuji

    2018-04-01

    One-pot sequential reactions using the acyl moieties installed by enzymatic dynamic kinetic resolution of alcohols have been little investigated. In this work, the acryloyl moiety installed via the lipase/oxovanadium combo-catalyzed dynamic kinetic resolution of a racemic dienol [4-(cyclohex-1-en-1-yl)but-3-en-2-ol or 1-(cyclohex-1-en-1-yl)but-2-en-1-ol] with a (Z)-3-(phenylsulfonyl)acrylate underwent an intramolecular Diels-Alder reaction in a one-pot procedure to produce an optically active naphtho[2,3-c]furan-1(3H)-one derivative (98% ee). This method was successfully applied to the asymmetric total synthesis of (-)-himbacine. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Practical Aspects and Mechanism of Asymmetric Hydrogenation with Chiral Half-Sandwich Complexes

    Czech Academy of Sciences Publication Activity Database

    Václavík, J.; Šot, P.; Vilhanová, B.; Pecháček, J.; Kuzma, Marek; Kačer, P.

    2013-01-01

    Roč. 18, č. 6 (2013), s. 6804-6828 ISSN 1420-3049 R&D Projects: GA ČR GA104/09/1497; GA ČR GAP106/12/1276 Institutional support: RVO:61388971 Keywords : asymmetric hydrogenation * ruthenium * reaction conditions Subject RIV: CC - Organic Chemistry Impact factor: 2.095, year: 2013

  9. Enantioselective solvent-free Robinson annulation reactions

    Indian Academy of Sciences (India)

    Unknown

    solvents to effect an asymmetric synthesis is an important step forward towards ... In continuation of our preliminary communication 2, we wish to ..... formation of chiral enamine 74 from the reaction of S-proline with pro-R carbonyl group.

  10. Heavy residues from very mass asymmetric heavy ion reactions

    International Nuclear Information System (INIS)

    Hanold, K.A.

    1994-08-01

    The isotopic production cross sections and momenta of all residues with nuclear charge (Z) greater than 39 from the reaction of 26, 40, and 50 MeV/nucleon 129 Xe + Be, C, and Al were measured. The isotopic cross sections, the momentum distribution for each isotope, and the cross section as a function of nuclear charge and momentum are presented here. The new cross sections are consistent with previous measurements of the cross sections from similar reaction systems. The shape of the cross section distribution, when considered as a function of Z and velocity, was found to be qualitatively consistent with that expected from an incomplete fusion reaction mechanism. An incomplete fusion model coupled to a statistical decay model is able to reproduce many features of these reactions: the shapes of the elemental cross section distributions, the emission velocity distributions for the intermediate mass fragments, and the Z versus velocity distributions. This model gives a less satisfactory prediction of the momentum distribution for each isotope. A very different model based on the Boltzman-Nordheim-Vlasov equation and which was also coupled to a statistical decay model reproduces many features of these reactions: the shapes of the elemental cross section distributions, the intermediate mass fragment emission velocity distributions, and the Z versus momentum distributions. Both model calculations over-estimate the average mass for each element by two mass units and underestimate the isotopic and isobaric widths of the experimental distributions. It is shown that the predicted average mass for each element can be brought into agreement with the data by small, but systematic, variation of the particle emission barriers used in the statistical model. The predicted isotopic and isobaric widths of the cross section distributions can not be brought into agreement with the experimental data using reasonable parameters for the statistical model

  11. Development of Low Energy Gap and Fully Regioregular Polythienylenevinylene Derivative

    Directory of Open Access Journals (Sweden)

    Tanya M. S. David

    2014-01-01

    Full Text Available Low energy gap and fully regioregular conjugated polymers find its wide use in solar energy conversion applications. This paper will first briefly review this type of polymers and also report synthesis and characterization of a specific example new polymer, a low energy gap, fully regioregular, terminal functionalized, and processable conjugated polymer poly-(3-dodecyloxy-2,5-thienylene vinylene or PDDTV. The polymer exhibited an optical energy gap of 1.46 eV based on the UV-vis-NIR absorption spectrum. The electrochemically measured highest occupied molecular orbital (HOMO level is −4.79 eV, resulting in the lowest unoccupied molecular orbital (LUMO level of −3.33 eV based on optical energy gap. The polymer was synthesized via Horner-Emmons condensation and is fairly soluble in common organic solvents such as tetrahydrofuran and chloroform with gentle heating. DSC showed two endothermic peaks at 67°C and 227°C that can be attributed to transitions between crystalline and liquid states. The polymer is thermally stable up to about 300°C. This polymer appears very promising for cost-effective solar cell applications.

  12. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim

    2013-11-01

    This review provides a comprehensive treatment of literature data dealing with asymmetric synthesis of α-amino-β-hydroxy and α,β-diamino acids via homologation of chiral Ni(II) complexes of glycine Schiff bases using aldol and Mannich-type reactions. These reactions proceed with synthetically useful chemical yields and thermodynamically controlled stereoselectivity and allow direct introduction of two stereogenic centers in a single operation with predictable stereochemical outcome. Furthermore, new application of Ni(II) complexes of α-amino acids Schiff bases for deracemization of racemic α-amino acids and (S) to (R) interconversion providing additional synthetic opportunities for preparation of enantiomerically pure α-amino acids, is also reviewed. Origin of observed diastereo-/enantioselectivity in the aldol, Mannich-type and deracemization reactions, generality and limitations of these methodologies are critically discussed.

  13. Asymmetric syntheses of 3,4-disubstituted tetrahydroquinoline derivatives using (+)- sparteine-mediated electrophilic substitution

    International Nuclear Information System (INIS)

    Choi, Yun Soo; Kang, Kyoung Hee; Park, Yong Sun

    2015-01-01

    Tetrahydroquinolines bearing substituents are frequently found as a substructure in a number of alkaloids and natural products. Since their individual stereoisomers displays different biological activities, it is desirable to develop a highly stereoselective synthetic method for tetrahydroquinolines. While some progress has recently been made toward the development of asymmetric synthetic methods for tetrahydroquinolines, it is still a challenging topic in organic synthesis. In order to investigate the source of diastereoselection attained in the substitution reaction with a racemic epoxide, we examined the substitution of 2 with an excess amount of racemic p-chlorophenyl-substituted oxirane. We have developed a novel method for the asymmetric synthesis of trans-3,4-diaryl-substituted tetrahy- droquinolines from ortho-substituted N-pivaloyl anilines. The enantioselective process includes (+)-sparteine-mediated stereoselective lithiati on, kinetic resolution of epoxides in substitution, and stereospecific Mitsu nobu cyclization as the key reactions. The simple protocol can provide highly functionalized tetrahydroqu inoline rings and would allow their further functionalization to access more complex target molecules

  14. Asymmetric syntheses of 3,4-disubstituted tetrahydroquinoline derivatives using (+)- sparteine-mediated electrophilic substitution

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Yun Soo; Kang, Kyoung Hee; Park, Yong Sun [Dept. of Chemistry, Konkuk University, Seoul (Korea, Republic of)

    2015-05-15

    Tetrahydroquinolines bearing substituents are frequently found as a substructure in a number of alkaloids and natural products. Since their individual stereoisomers displays different biological activities, it is desirable to develop a highly stereoselective synthetic method for tetrahydroquinolines. While some progress has recently been made toward the development of asymmetric synthetic methods for tetrahydroquinolines, it is still a challenging topic in organic synthesis. In order to investigate the source of diastereoselection attained in the substitution reaction with a racemic epoxide, we examined the substitution of 2 with an excess amount of racemic p-chlorophenyl-substituted oxirane. We have developed a novel method for the asymmetric synthesis of trans-3,4-diaryl-substituted tetrahy- droquinolines from ortho-substituted N-pivaloyl anilines. The enantioselective process includes (+)-sparteine-mediated stereoselective lithiati on, kinetic resolution of epoxides in substitution, and stereospecific Mitsu nobu cyclization as the key reactions. The simple protocol can provide highly functionalized tetrahydroqu inoline rings and would allow their further functionalization to access more complex target molecules.

  15. Ring-Contraction Strategy for the Practical, Scalable, Catalytic Asymmetric Synthesis of Versatile γ-Quaternary Acylcyclopentenes

    KAUST Repository

    Hong, Allen Y.

    2011-02-24

    Contraction action! A simple protocol for the catalytic asymmetric synthesis of highly functionalized γ-quaternary acylcyclopentenes (see schematic) in up to 91 % overall yield and 92 % ee has been developed. The reaction sequence employs a palladium-catalyzed enantioselective alkylation reaction and exploits the unusual stability of β-hydroxy cycloheptanones to achieve a general and robust method for performing two-carbon ring contractions.

  16. Ring-Contraction Strategy for the Practical, Scalable, Catalytic Asymmetric Synthesis of Versatile γ-Quaternary Acylcyclopentenes

    KAUST Repository

    Hong, Allen Y.; Krout, Michael R.; Jensen, Thomas; Bennett, Nathan B.; Harned, Andrew M.; Stoltz, Brian M.

    2011-01-01

    Contraction action! A simple protocol for the catalytic asymmetric synthesis of highly functionalized γ-quaternary acylcyclopentenes (see schematic) in up to 91 % overall yield and 92 % ee has been developed. The reaction sequence employs a palladium-catalyzed enantioselective alkylation reaction and exploits the unusual stability of β-hydroxy cycloheptanones to achieve a general and robust method for performing two-carbon ring contractions.

  17. Directed transverse flow and its disappearance for asymmetric reactions

    International Nuclear Information System (INIS)

    Lovejot; Gautam, S.

    2014-01-01

    We study the directed transverse flow for mass asymmetry reactions. This is done by keeping the target fixed and varying the projectile mass from 4 He to 131 Xe. We find that directed transverse flow is sensitive to the mass of the projectile. We also study the disappearance of flow at a particular impact parameter called Geometry of Vanishing Flow (GVF) for such mass asymmetry reactions. Our results indicate that GVF is sensitive to the beam energy as well as to the mass of the projectile.

  18. Polystyrene-supported cu(II)-R-Box as recyclable catalyst in asymmetric Friedel–Crafts reaction

    KAUST Repository

    Desyatkin, V. G.

    2017-02-12

    The complex of copper(II) trifluoromethanesulfonate with chiral isopropyl bis(oxazoline) ligand (i-Pr-Box) was immobilized on accessible and inexpensive Merrifield resin according to a “click” procedure. The resulting catalyst showed high efficiency and recyclability in the asymmetric Friedel–Crafts alkylation of indole and its derivatives. The catalyst can be recycled five times without appreciable loss in activity and enantioselectivity.

  19. Polystyrene-supported cu(II)-R-Box as recyclable catalyst in asymmetric Friedel–Crafts reaction

    KAUST Repository

    Desyatkin, V. G.; Anokhin, M. V.; Rodionov, Valentin; Beletskaya, I. P.

    2017-01-01

    The complex of copper(II) trifluoromethanesulfonate with chiral isopropyl bis(oxazoline) ligand (i-Pr-Box) was immobilized on accessible and inexpensive Merrifield resin according to a “click” procedure. The resulting catalyst showed high efficiency and recyclability in the asymmetric Friedel–Crafts alkylation of indole and its derivatives. The catalyst can be recycled five times without appreciable loss in activity and enantioselectivity.

  20. Organocatalytic asymmetric michael addition of aldehydes to beta-nitroacroleine dimethyl acetal.

    Science.gov (United States)

    Reyes, Efraim; Vicario, Jose L; Badía, Dolores; Carrillo, Luisa

    2006-12-21

    [Structure: see text] The organocatalytic asymmetric Michael addition of aldehydes to beta-nitroacroleine dimethyl acetal has been studied in detail. The reaction took place with excellent yields and high stereoselectivities when a chiral beta-amino alcohol such as L-prolinol was employed as the catalyst, leaving a formation of highly functionalized enantioenriched compounds containing two differentiated formyl groups together with a nitro moiety.

  1. A DFT investigation on interactions between asymmetric derivatives of cisplatin and nucleobase guanine

    Science.gov (United States)

    Tai, Truong Ba; Nhat, Pham Vu

    2017-07-01

    The interactions of hydrolysis products of cisplatin and its asymmetric derivatives cis- and trans-[PtCl2(iPram)(Mepz)] with guanine were studied using DFT methods. These interactions are dominated by electrostatic effects, namely hydrogen bond contributions and there exists a charge flow from H-atoms of ligands to the O-atoms of guanine. The replacement of NH3 moieties by larger functional groups accompanies with a moderate reaction between PtII and guanine molecule, diminishing the cytotoxicity of the drug. The asymmetric and symmetric NH2 stretching modes of complexes having strong hydrogen bond interactions are red shifted importantly as compared to complexes without presence of hydrogen bond interactions.

  2. Does asymmetric correlation affect portfolio optimization?

    Science.gov (United States)

    Fryd, Lukas

    2017-07-01

    The classical portfolio optimization problem does not assume asymmetric behavior of relationship among asset returns. The existence of asymmetric response in correlation on the bad news could be important information in portfolio optimization. The paper applies Dynamic conditional correlation model (DCC) and his asymmetric version (ADCC) to propose asymmetric behavior of conditional correlation. We analyse asymmetric correlation among S&P index, bonds index and spot gold price before mortgage crisis in 2008. We evaluate forecast ability of the models during and after mortgage crisis and demonstrate the impact of asymmetric correlation on the reduction of portfolio variance.

  3. 2,5-Bis{2,2-bis[4-(dimethylaminophenyl]ethenyl}-N,N′-diphenyl-N,N′-dipropylbenzene-1,4-diamine

    Directory of Open Access Journals (Sweden)

    Volker Schmitt

    2011-04-01

    Full Text Available The title compound, C60H68N6, was prepared by Horner olefination of a terephthaldialdehyde and a diarylmethyl phosphonate. There is one half-molecule, located on an inversion centre, in the asymmetric unit. The dihedral angle between the plane of the vinylene unit and the central ring is 36.79 (15°, while those between the vinylene unit and the lateral phenyl rings are 53.04 (10 and 53.74 (9°.

  4. Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

    International Nuclear Information System (INIS)

    Lewis, Alan M.; Manolopoulos, David E.; Hore, P. J.

    2014-01-01

    We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a “proof of principle” for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C ·+ PF ·− radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical

  5. Aqueous based asymmetrical-bipolar electrochemical capacitor with a 2.4 V operating voltage

    Science.gov (United States)

    Wu, Haoran; Lian, Keryn

    2018-02-01

    A novel asymmetrical-bipolar electrochemical capacitor system leveraging the contributions of a Zn-CNT asymmetrical electrode and a KOH-H2SO4 dual-pH electrolyte was developed. The positive and negative electrodes operated in electrolytes with different pH, exploiting the maximum potential of both electrodes, which led to a cell voltage of 2.4 V. The potential tracking of both electrodes revealed that the Zn negative electrode could maintain a potential at -1.2 V, while the CNT positive electrode can be charged to +1.2 V without significant irreversible reactions. A bipolar ion exchange membrane has effectively separated the acid and alkaline from neutralization, which resulted in stable performance of the device with capacitance retention of 94% and coulombic efficiency of 99% over 10,000 cycles. This asymmetrical-bipolar design overcomes the thermodynamic limit of water decomposition, opening a new avenue towards high energy and high power density aqueous-based ECs.

  6. Reactivity differences of Pt0 phosphine complexes in C-C bond activation of asymmetric acetylenes

    NARCIS (Netherlands)

    Gunay, A.; Müller, C.; Lachicotte, R.J.; Brennessel, W.W.; Jones, W.D.

    2009-01-01

    Carbon-carbon bond activation reactions of asymmetric acetylene derivatives of the type L2Pt(PhC=CR) were studied with 1,2-bis(diisopropylphosphino)ethane (dippe), 1,2-bis(di-tert-butylphosphino)ethane (dtbpe), and 1-diisopropylphosphino-2-dimethylaminoethane (dippdmae) chelates.

  7. Early Universe synthesis of asymmetric dark matter nuggets

    Science.gov (United States)

    Gresham, Moira I.; Lou, Hou Keong; Zurek, Kathryn M.

    2018-02-01

    We compute the mass function of bound states of asymmetric dark matter—nuggets—synthesized in the early Universe. We apply our results for the nugget density and binding energy computed from a nuclear model to obtain analytic estimates of the typical nugget size exiting synthesis. We numerically solve the Boltzmann equation for synthesis including two-to-two fusion reactions, estimating the impact of bottlenecks on the mass function exiting synthesis. These results provide the basis for studying the late Universe cosmology of nuggets in a future companion paper.

  8. Constructing Asymmetric Polyion Complex Vesicles via Template Assembling Strategy: Formulation Control and Tunable Permeability

    Directory of Open Access Journals (Sweden)

    Junbo Li

    2017-11-01

    Full Text Available A strategy for constructing polyion complex vesicles (PICsomes with asymmetric structure is described. Poly(methylacrylic acid-block-poly(N-isopropylacrylamide modified gold nanoparticles (PMAA-b-PNIPAm-@-Au NPs were prepared and then assembled with poly(ethylene glycol-block-poly[1-methyl-3-(2-methacryloyloxy propylimidazolium bromine] (PEG-b-PMMPImB via polyion complex of PMMA and PMMPImB. After removing the Au NPs template, asymmetric PICsomes composed of a PNIPAm inner-shell, PIC wall, and PEG outer-corona were obtained. These PICsomes have low protein absorption and thermally tunable permeability, provided by the PEG outer-corona and the PNIPAm inner-shell, respectively. Moreover, PICsome size can be tailored by using templates of predetermined sizes. This novel strategy for constructing asymmetric PICsomes with well-defined properties and controllable size is valuable for applications such as drug delivery, catalysis and monitoring of chemical reactions, and biomimetics.

  9. Toward a psychology of humiliation in asymmetric conflict.

    Science.gov (United States)

    McCauley, Clark

    2017-04-01

    Humiliation is often cited in attempts to understand the origins of asymmetric conflicts, especially conflicts involving terrorism. This article reviews common usage, expert opinion, and experiences in interpersonal and intergroup conflicts to suggest a construct definition of humiliation as a combination of anger and shame. Following appraisal theory, this definition distinguishes between the situational appraisals associated with humiliation (insult and injury; failure to retaliate) and the emotional experience of humiliation (in which the combination of anger and shame may be more synergism than summation). Research on humiliation has barely begun and focuses on interpersonal relations; a crucial issue is whether interpersonal humiliation is the same experience as the intergroup humiliation salient in accounts of terrorism and terrorists. Also important is the prediction that the targets of terrorist attack will experience humiliation if the terrorists are unknown or unreachable; thus failure to retaliate may humiliate the strong as well as the weak in asymmetric conflict. Better understanding of humiliation may be useful for understanding both terrorist violence and government reactions to this violence. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  10. Charge Asymmetric Cosmic Rays as a probe of Flavor Violating Asymmetric Dark Matter

    DEFF Research Database (Denmark)

    Masina, Isabella; Sannino, Francesco

    2011-01-01

    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....

  11. Biomimetically inspired asymmetric total synthesis of (+)-19-dehydroxyl arisandilactone A

    Science.gov (United States)

    Han, Yi-Xin; Jiang, Yan-Long; Li, Yong; Yu, Hai-Xin; Tong, Bing-Qi; Niu, Zhe; Zhou, Shi-Jie; Liu, Song; Lan, Yu; Chen, Jia-Hua; Yang, Zhen

    2017-01-01

    Complex natural products are a proven and rich source of disease-modulating drugs and of efficient tools for the study of chemical biology and drug discovery. The architectures of complex natural products are generally considered to represent significant barriers to efficient chemical synthesis. Here we describe a concise and efficient asymmetric synthesis of 19-dehydroxyl arisandilactone A--which belongs to a family of architecturally unique, highly oxygenated nortriterpenoids isolated from the medicinal plant Schisandra arisanensis. This synthesis takes place by means of a homo-Michael reaction, a tandem retro-Michael/Michael reaction, and Cu-catalysed intramolecular cyclopropanation as key steps. The proposed mechanisms for the homo-Michael and tandem retro-Michael/Michael reactions are supported by density functional theory (DFT) calculation. The developed chemistry may find application for the synthesis of its other family members of Schisandraceae nortriterpenoids.

  12. Probabilities of symmetric and asymmetric fission in the proton bombardment of Th{sup 232}

    Energy Technology Data Exchange (ETDEWEB)

    Bowles, B J [Atomic Energy Research Establishment, Chemistry Div., Harwell (United Kingdom); Brown, F; Butler, J P

    1957-08-01

    The ratio of symmetric to asymmetric fission in the proton bombardment of Th{sup 232} does not rise steadily with increasing proton energy; a periodic decrease in superposed upon the over-all increase. This is attributed to the changing pattern of various fission reactions, (p,f), (p,nf), etc. (author)

  13. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 3: Michael addition reactions and miscellaneous transformations.

    Science.gov (United States)

    Aceña, José Luis; Sorochinsky, Alexander E; Soloshonok, Vadim

    2014-09-01

    The major goal of this review is a critical discussion of the literature data on asymmetric synthesis of α-amino acids via Michael addition reactions involving Ni(II)-complexes of amino acids. The material covered is divided into two conceptually different groups dealing with applications of: (a) Ni(II)-complexes of glycine as C-nucleophiles and (b) Ni(II)-complexes of dehydroalanine as Michael acceptors. The first group is significantly larger and consequently subdivided into four chapters based on the source of stereocontrolling element. Thus, a chiral auxiliary can be used as a part of nucleophilic glycine Ni(II) complex, Michael acceptor or both, leading to the conditions of matching vs. mismatching stereochemical preferences. The particular focus of the review is made on the practical aspects of the methodology under discussion and mechanistic considerations.

  14. Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

    Directory of Open Access Journals (Sweden)

    Worawan Bhanthumnavin

    2010-02-01

    Full Text Available Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of α-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related α-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005–2009.

  15. Intensification of the Use of Ionic Liquids as Efficient Reaction Co-Solvents in Asymmetric Hydrogenations

    Czech Academy of Sciences Publication Activity Database

    Černá, I.; Klusoň, Petr; Bendová, Magdalena; Floriš, Tomáš; Pelantová, Helena; Pekárek, T.

    2011-01-01

    Roč. 50, č. 3 (2011), s. 264-272 ISSN 0255-2701 R&D Projects: GA AV ČR KAN400720701; GA AV ČR IAA400720710 Institutional research plan: CEZ:AV0Z40720504; CEZ:AV0Z50200510 Keywords : Ionic liquids * asymmetric hydrogenations * BmimPF6 Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.924, year: 2011

  16. A comparative Study of C2-Symmetric Bis(aziridine) Ligands in Some Transition Metal-Mediated Asymmetric Transformations

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Johansson, Fredrik; Harden, Adrian

    1998-01-01

    A comparative study has been made of the performance of differently substituted Ca-symmetric bis(aziridine) ligands in a variety of metal-mediated asymmetric reactions. The metals studied were osmium (dihydroxylation), palladium (allylic alkylation) and copper (cyclopropanation and aziridination...

  17. Synthesis method of asymmetric gold particles.

    Science.gov (United States)

    Jun, Bong-Hyun; Murata, Michael; Hahm, Eunil; Lee, Luke P

    2017-06-07

    Asymmetric particles can exhibit unique properties. However, reported synthesis methods for asymmetric particles hinder their application because these methods have a limited scale and lack the ability to afford particles of varied shapes. Herein, we report a novel synthetic method which has the potential to produce large quantities of asymmetric particles. Asymmetric rose-shaped gold particles were fabricated as a proof of concept experiment. First, silica nanoparticles (NPs) were bound to a hydrophobic micro-sized polymer containing 2-chlorotritylchloride linkers (2-CTC resin). Then, half-planar gold particles with rose-shaped and polyhedral structures were prepared on the silica particles on the 2-CTC resin. Particle size was controlled by the concentration of the gold source. The asymmetric particles were easily cleaved from the resin without aggregation. We confirmed that gold was grown on the silica NPs. This facile method for synthesizing asymmetric particles has great potential for materials science.

  18. Recent Progress in Asymmetric Catalysis and Chromatographic Separation by Chiral Metal–Organic Frameworks

    Directory of Open Access Journals (Sweden)

    Suchandra Bhattacharjee

    2018-03-01

    Full Text Available Metal–organic frameworks (MOFs, as a new class of porous solid materials, have emerged and their study has established itself very quickly into a productive research field. This short review recaps the recent advancement of chiral MOFs. Here, we present simple, well-ordered instances to classify the mode of synthesis of chiral MOFs, and later demonstrate the potential applications of chiral MOFs in heterogeneous asymmetric catalysis and enantioselective separation. The asymmetric catalysis sections are subdivided based on the types of reactions that have been successfully carried out recently by chiral MOFs. In the part on enantioselective separation, we present the potentiality of chiral MOFs as a stationary phase for high-performance liquid chromatography (HPLC and high-resolution gas chromatography (GC by considering fruitful examples from current research work. We anticipate that this review will provide interest to researchers to design new homochiral MOFs with even greater complexity and effort to execute their potential functions in several fields, such as asymmetric catalysis, enantiomer separation, and chiral recognition.

  19. Recent results on fusion and direct reactions with weakly bound stable nuclei

    International Nuclear Information System (INIS)

    Shrivastava, A.

    2011-01-01

    Recent measurements of fusion and direct reactions in case of weakly bound stable nuclei at extreme sub-barrier energies using a sensitive off beam technique are presented. First section deals with deep sub-barrier fusion cross-section measurement for 67 Li + 198 Pt followed by the study of fragment capture reaction of 7 Li + 198 Pt. Deviation in the slope of the fusion excitation function, as observed in case of medium heavy systems, is absent in the present asymmetric systems at these low energies. This study shows the absence of fusion hindrance, suggesting modifications in models that explain deep sub-barrier fusion data to incorporate weakly bound asymmetric systems

  20. Instantaneous Tunneling Flight Time for Wavepacket Transmission through Asymmetric Barriers.

    Science.gov (United States)

    Petersen, Jakob; Pollak, Eli

    2018-04-12

    The time it takes a particle to tunnel through the asymmetric Eckart barrier potential is investigated using Gaussian wavepackets, where the barrier serves as a model for the potential along a chemical reaction coordinate. We have previously shown that the, in principle experimentally measurable, tunneling flight time, which determines the time taken by the transmitted particle to traverse the barrier, vanishes for symmetric potentials like the Eckart and square barrier [ Petersen , J. ; Pollak , E. J. Phys. Chem. Lett. 2017 , 9 , 4017 ]. Here we show that the same result is obtained for the asymmetric Eckart barrier potential, and therefore, the zero tunneling flight time seems to be a general result for one-dimensional time-independent potentials. The wavepacket dynamics is simulated using both an exact quantum mechanical method and a classical Wigner prescription. The excellent agreement between the two methods shows that quantum coherences are not important in pure one-dimensional tunneling and reinforces the conclusion that the tunneling flight time vanishes.

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

    Science.gov (United States)

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

    2015-06-08

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Variational Flooding Study of a SN2 Reaction.

    Science.gov (United States)

    Piccini, GiovanniMaria; McCarty, James J; Valsson, Omar; Parrinello, Michele

    2017-02-02

    We have studied the reaction dynamics of a prototypical organic reaction using a variationally optimized truncated bias to accelerate transitions between educt and product reactant states. The asymmetric S N 2 nucleophilic substitution reaction of fluoromethane and chloromethane CH 3 F + Cl - ⇌ CH 3 Cl + F - is considered, and many independent biased molecular dynamics simulations have been performed at 600, 900, and 1200 K, collecting several hundred transitions at each temperature. The transition times and relative rate constants have been obtained for both reaction directions. The activation energies extracted from an Arrhenius plot compare well with standard static calculations.

  3. Dynamic response of the ITER tokamak during asymmetric VDEs

    International Nuclear Information System (INIS)

    Schioler, Tyge; Bachmann, Christian; Mazzone, Giuseppe; Sannazzaro, Giulio

    2011-01-01

    During the operational life of ITER, it is expected that a number of vertical displacement events (VDEs) will occur. A sub-class of these events, 'slow' asymmetric VDEs, is of particular interest from a structural point of view. This is because the forces generated during such events are both substantial and sufficiently long-lasting to significantly excite the structure. It is necessary to establish that the absolute and relative displacements of components, as well as internal and external forces, stay within acceptable limits during these events. Previous studies have investigated this problem using relatively simple models and non-rotating loads. A new, more detailed, 360-degree model was developed, and used to assess the effects of asymmetric VDEs. This paper presents the main results of this investigation. It is shown that the distance between the VV and the TFC at the inboard wall can decrease by as much as 19 mm at the equatorial plane, and that the vertical reaction force in the Vacuum Vessel supports can reach 15 MN.

  4. Intramolecular and Transannular Diels-Alder Reactions

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Ascic, Erhad

    2014-01-01

    Few reactions can compete with the Diels-Alder (DA) [4+2] cycloaddition for the rapid and efficient generation of molecular complexity. The DA reaction is atom-economic and stereospecific, as well as diastereo- and regioselective. The intramolecular version (IMDA) of the DA cycloaddition and its...... and dienophile, methods for acceleration of IMDA reactions (such as use of high pressure) and catalysis (using oxophilic or carbophilic metal complexes, Brønsted acids, and enzymes). The use of furans as diene components (IMDAF), intramolecular hetero-DA (IMHDA) and IMDA reactions with inverse electron demand...... are also covered. Applications of IMDA to asymmetric synthesis (from substrate control through to enantioselective catalysis, including organocatalysis) are presented, along with tandem sequences involving IMDA cycloaddition. A theme pervading the whole chapter is the use of IMDA reactions for the total...

  5. Monolayer Nickel Cobalt Hydroxyl Carbonate for High Performance All-Solid-State Asymmetric Supercapacitors.

    Science.gov (United States)

    Zhao, Yufeng; Ma, Hongnan; Huang, Shifei; Zhang, Xuejiao; Xia, Meirong; Tang, Yongfu; Ma, Zi-Feng

    2016-09-07

    The emergence of atomically thick nanolayer materials, which feature a short ion diffusion channel and provide more exposed atoms in the electrochemical reactions, offers a promising occasion to optimize the performance of supercapacitors on the atomic level. In this work, a novel monolayer Ni-Co hydroxyl carbonate with an average thickness of 1.07 nm is synthesized via an ordinary one-pot hydrothermal route for the first time. This unique monolayer structure can efficiently rise up the exposed electroactive sites and facilitate the surface dependent electrochemical reaction processes, and thus results in outstanding specific capacitance of 2266 F g(-1). Based on this material, an all-solid-state asymmetric supercapacitor is developed adopting alkaline PVA (poly(vinyl alcohol)) gel (PVA/KOH) as electrolyte, which performs remarkable cycling stability (no capacitance fade after 19 000 cycles) together with promising energy density of 50 Wh kg(-1) (202 μWh cm(-2)) and high power density of 8.69 kW kg(-1) (35.1 mW cm(-2)). This as-assembled all-solid-state asymmetric supercapacitor (AASC) holds great potential in the field of portable energy storage devices.

  6. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei; Tang, Yurong; Atodiresei, Iuliana; Rueping, Magnus

    2016-01-01

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields

  7. Highly selective sulfur ylide mediated asymmetric epoxidations and aziridinations using an inexpensive chiral sulfide and applications to the synthesis of quinine and quinidine (abstract)

    International Nuclear Information System (INIS)

    Arshad, M.; Illa, O.; Mcgarrigle, E.M.

    2011-01-01

    Asymmetric sulfur ylide mediated epoxidation, which is considered a complimentary method to asymmetric epoxidation of alkene has been utilized as a key step in the asymmetric total synthesis of complex cinchona alkaloids quinine and quinidine. Isothiocineole 1, which was readily available in one step from very inexpensive starting materials, is employed as a chiral sulfide to prepare the desired sulfonium salt 2. The semi-stabilised ylide derived from this salt on epoxidation with meroquinene aldehyde 3, afforded the required epoxide 4 in 81% yield and 89:11 diastereoselectivity (trans/cis). The epoxide was converted to the target quinine 5 in 73% yield over four steps in one pot. Similarly, the opposite enantiomer of isothiocineole was used to synthesise the corresponding sulfonium salt, which on reaction with meroquinene aldehyde gave epoxide in 73% yield and 84:16 diastereoselectivity (trans/cis). This epoxide was transformed to the target quinidine in 78% yield over four steps in one pot. The epoxidation reactions proceeded under reagent control with high trans selectivity. The effect of sulfide and ylide substituents on the stereochemical outcome of the epoxidation reaction is also prescribed. (author)

  8. Asymmetric Evolutionary Games

    Science.gov (United States)

    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

  9. Asymmetrical field emitter

    Science.gov (United States)

    Fleming, J.G.; Smith, B.K.

    1995-10-10

    A method is disclosed for 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. 17 figs.

  10. Asymmetrical distorted structure, dynamics, and reactions of the silacyclohexane and related radical cations: ESR and ab-initio MO study

    International Nuclear Information System (INIS)

    Komaguchi, Kenji; Shiotani, Masaru; Ishikawa, Mitsuo

    1995-01-01

    The σ-type radical cations generated by one electron oxidation of the saturated hydrocarbon have been attracted much attention because of their fundamental importance as primary reactant species in radiation chemistry. Our studies on σ-type radical cations were recently extended to the silacyclohexane (cSiC5), silacyclopentane (cSiC4), and silacyclobutane (cSiC3) radical cations. Their electronic structure, dynamics, and reactions were investigated by means of low temperature matrix isolation ESR technique combined with ionizing radiation (γ-rays from 60 Co). In the preceding paper, the 1-methylsilacyclohexane (1-Me-cSiC5) radical cation has been found to take an asymmetrically distorted C 1 structure with one of two Si-C bonds elongated in which the unpaired electron mainly resides ( 2 A in C 1 ). This conclusion was based on the 4.2 K ESR spectra of radical cations of selectively deuteriated and/or methylsubstituted silacyclohexanes, i.e., cSiC5-2,2,6,6-d 4 + , 1-Me-cSiC5 + , 1-Me-cSiC5-2,2-d 2 + , 1-Me-cSiC5-2,2,6,6-d 4 + , 1,1-Me 2 -cSiC5 + , and 4,4-Me 2 -cSiC5 + , in a frozen CF 3 -cC 6 F 11 matrix. Here we report further experimental and theoretical results on 1-methylsilacyclohexane radical cation, especially on the ab initio MO results and matrix effects on the structural distortion, as well as thermal reactions of the radical cations. The results will make it clear that the distorted C 1 structure of the 1-Me-cSiC5 + is the intrinsic nature at the ground electronic state. (J.P.N.)

  11. Chiral four-membered cyclic nitrones; asymmetric induction in the (4+2)-cycloaddition reaction of chiral ynamines and nitroalkenes

    NARCIS (Netherlands)

    van Elburg, P.A.; Honig, G.W.N.; Reinhoudt, David

    1987-01-01

    Chiral four-membered cyclic nitrones were synthesized by the asymmetric (4+2)-cycloaddition of nitroalkenes 1 and chiral ynamines 2. The subsequent stereoselective addition of nucleophiles to these nitrones enabled the synthesis of chiral N-hydroxyazetidines.

  12. Differential isospin-fractionation in dilute asymmetric nuclear matter

    International Nuclear Information System (INIS)

    Li Baoan; Chen Liewen; Ma Hongru; Xu Jun; Yong Gaochan

    2007-01-01

    The differential isospin-fractionation (IsoF) during the liquid-gas phase transition in dilute asymmetric nuclear matter is studied as a function of nucleon momentum. Within a self-consistent thermal model it is shown that the neutron/proton ratio of the gas phase becomes smaller than that of the liquid phase for energetic nucleons, although the gas phase is overall more neutron-rich. Clear indications of the differential IsoF consistent with the thermal model predictions are demonstrated within a transport model for heavy-ion reactions. Future comparisons with experimental data will allow us to extract critical information about the momentum dependence of the isovector strong interaction

  13. Efficient Asymmetric Synthesis of S,S-2-methylsulfanyl-2-methylsulfinyl-1-indanone

    OpenAIRE

    Derisvaldo Rosa Paiva; Roberto da Silva Gomes

    2013-01-01

    Diastereoselective synthesis of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanol by reduction of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanone optically enriched demonstrating to be highly efficiency using the sulfanyl group as asymmetric induction control agent during an addition reaction to carbonyl group.The 2-methylsulfinyl-1-indanone was obtained for the first time in one unique step without further oxidation steps. The synthesis of SR, SS of 2-methylsulphinyl-1-indanone optically enrich...

  14. Studies Toward the Asymmetric Synthesis of the Right Part of the Mycalamides

    OpenAIRE

    Zhong, H. Marlon; Sohn, Jeong-Hun; Rawal, Viresh H.

    2007-01-01

    Described herein is the asymmetric synthesis of a functionalized, trioxadecalin unit that comprises the right-hand part of the mycalamides and related natural products. The synthetic route involves a 16-step sequence that accomplishes the formation of two heterocyclic rings and the generation of five stereocenters. The synthesis commenced with a C2 symmetric starting material, diethyl D-tartrate, and took advantage of a relay of diastereoselective reactions to extend this four-carbon chain an...

  15. Investigation of heterogeneous asymmetric dihydroxylation over OsO{sub 4}-(QN){sub 2}PHAL catalysts of functionalized bimodal mesoporous silica with ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, Shenjie [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Sun, Jihong, E-mail: jhsun@bjut.edu.cn [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Li, Yuzhen; Gao, Lin [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China)

    2011-08-15

    Highlights: {yields} Functionalized bimodal mesoporous silica with MTMSPIm{sup +}Cl{sup -}. {yields} Mesoporous catalyst immobilized with OsO{sub 4}-(QN){sub 2}PHAL. {yields} Catalysts for asymmetric dihydroxylation reaction with high yield and enatioselectivity. {yields} Recyclable catalysts. -- Abstract: A novel synthesis of the functionalized bimodal mesoporous silica with ionic liquid (FBMMs) was performed. After grafting 1-methyl-3-(trimethoxysilyl)propylimidazolium chloride onto the surface of bimodal mesoporous silicas, 1,4-bis(9-O-quininyl)phthalazine ((QN){sub 2}-PHAL) and K{sub 2}Os(OH){sub 4}.2H{sub 2}O were immobilized onto the modified FBMMs by adsorption or ionic exchange methods, and then, the asymmetric dihydroxylation reaction was carried out by using solid catalysts. Techniques such as X-ray diffraction, Fourier Transform Infrared spectroscopy, N{sub 2} adsorption and desorption were employed to characterize their structure and properties. The results showed that the mesoporous ordering degree of bimodal mesoporous silica decreased after functionalization and immobilization of OsO{sub 4}-(QN){sub 2}PHAL. Being very effective in asymmetric dihydroxylation with high yield and enantioselectivity, the prepared heterogeneous solid catalyst could be recycled for five times with little loss of enantioselectivity, with comparison of those results obtained in homophase system. Moreover, the effect of Osmium catalyst on asymmetric dihydroxylation was investigated.

  16. High Flux Heat Exchanger

    Science.gov (United States)

    1993-01-01

    maximum jet velocity (6.36 m/s), and maximum number of jets (nine). Wadsworth and Mudawar [49] describe the use of a single slotted nozzle to provide...H00503 (ASME), pp. 121-128, 1989. 40 49. D. C. Wadsworth and I. Mudawar , "Cooling of a Multichip Electronic Module by Means of Confined Two-Dimensional...Jets of Dielectric Liquid," HTD-Vol. 111, Heat Transfer in Electrglif, Book No. H00503 (ASME), pp. 79-87, 1989. 50. D.C. Wadsworth and I. Mudawar

  17. Alternative Asymmetric Stochastic Volatility Models

    NARCIS (Netherlands)

    M. Asai (Manabu); M.J. McAleer (Michael)

    2010-01-01

    textabstractThe stochastic volatility model usually incorporates asymmetric effects by introducing the negative correlation between the innovations in returns and volatility. In this paper, we propose a new asymmetric stochastic volatility model, based on the leverage and size effects. The model is

  18. Asymmetric ion trap

    Science.gov (United States)

    Barlow, Stephan E.; Alexander, Michael L.; Follansbee, James C.

    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.

  19. Synthesis of New Chiral Ligands Based on Thiophene Derivatives for Use in Catalytic Asymmetric Oxidation of Sulfides

    International Nuclear Information System (INIS)

    Jeong, Yong Chul; Ahn, Dae Jun; Lee, Woo Sun; Lee, Seung Han; Ahn, Kwang Hyun

    2011-01-01

    We discovered that the vanadium complexes of new Schiff base ligands and prepared from thiophene derivatives efficiently catalyze the asymmetric oxidation of sulfides by hydrogen peroxide to provide sulfoxides with enantioselectivities up to 79% ee and in yields up to 89%. Notably, Schiff base showed better or similar enantioselectivity than the well-studied Schiff base. These results suggest possible applications of Schiff bases derived from and in other catalytic asymmetric reactions. Chiral sulfoxides are important functional groups for various applications. For example, the biological activities of sulfoxide containing drugs such as omeprazole are strongly related to the chirality of the sulfoxide group; for this reason, esomeprazole, the enantiomerically pure form of omeprazole, was later developed. There are several chiral sulfoxide based drugs that have been introduced by the pharmaceutical industry including armodafinil, aprikalim, oxisurane, and ustiloxin. Chiral sulfoxides have also been utilized as chiral auxiliaries in asymmetric syntheses of chiral intermediates

  20. Asymmetric split-ring resonator-based biosensor for detection of label-free stress biomarkers

    Science.gov (United States)

    Lee, Hee-Jo; Lee, Jung-Hyun; Choi, Suji; Jang, Ik-Soon; Choi, Jong-Soon; Jung, Hyo-Il

    2013-07-01

    In this paper, an asymmetric split-ring resonator, metamaterial element, is presented as a biosensing transducer for detection of highly sensitive and label-free stress biomarkers. In particular, the two biomarkers, cortisol and α-amylase, are used for evaluating the sensitivity of the proposed biosensor. In case of cortisol detection, the competitive reaction between cortisol-bovine serum albumin and free cortisol is employed, while alpha-amylase is directly detected by its antigen-antibody reaction. From the experimental results, we find that the limit of detection and sensitivity of the proposed sensing device are about 1 ng/ml and 1.155 MHz/ng ml-1, respectively.

  1. Fluoride-induced modulation of ionic transport in asymmetric nanopores functionalized with "caged" fluorescein moieties.

    Science.gov (United States)

    Ali, Mubarak; Ahmed, Ishtiaq; Ramirez, Patricio; Nasir, Saima; Cervera, Javier; Niemeyer, Christof M; Ensinger, Wolfgang

    2016-04-28

    We demonstrate experimentally and theoretically a nanofluidic fluoride sensing device based on a single conical pore functionalized with "caged" fluorescein moieties. The nanopore functionalization is based on an amine-terminated fluorescein whose phenolic hydroxyl groups are protected with tert-butyldiphenylsilyl (TBDPS) moieties. The protected fluorescein (Fcn-TBDPS-NH2) molecules are then immobilized on the nanopore surface via carbodiimide coupling chemistry. Exposure to fluoride ions removes the uncharged TBDPS moieties due to the fluoride-promoted cleavage of the silicon-oxygen bond, leading to the generation of negatively charged groups on the fluorescein moieties immobilized onto the pore surface. The asymmetrical distribution of these groups along the conical nanopore leads to the electrical rectification observed in the current-voltage (I-V) curve. On the contrary, other halides and anions are not able to induce any significant ionic rectification in the asymmetric pore. In each case, the success of the chemical functionalization and deprotection reactions is monitored through the changes observed in the I-V curves before and after the specified reaction step. The theoretical results based on the Nernst-Planck and Poisson equations further demonstrate the validity of an experimental approach to fluoride-induced modulation of nanopore current rectification behaviour.

  2. Worst Asymmetrical Short-Circuit Current

    DEFF Research Database (Denmark)

    Arana Aristi, Iván; Holmstrøm, O; Grastrup, L

    2010-01-01

    In a typical power plant, the production scenario and the short-circuit time were found for the worst asymmetrical short-circuit current. Then, a sensitivity analysis on the missing generator values was realized in order to minimize the uncertainty of the results. Afterward the worst asymmetrical...

  3. Do Daily Retail Gasoline Prices adjust Asymmetrically?

    Energy Technology Data Exchange (ETDEWEB)

    Bettendorf, L. [Tinbergen Instituut, Amsterdam/Rotterdam (Netherlands); Van der Geest, S. [Erasmus Universiteit, Rotterdam (Netherlands); Kuper, G. [University of Groningen, Groningen (Netherlands)

    2005-04-15

    This paper analyzes adjustments in the Dutch retail gasoline prices. We estimate an error correction model on changes in the daily retail price for gasoline (taxes excluded) for the period 1996-2004 taking care of volatility clustering by estimating an EGARCH model. It turns out the volatility process is asymmetrical: an unexpected increase in the producer price has a larger effect on the variance of the producer price than an unexpected decrease. We do not find strong evidence for amount asymmetry. However, there is a faster reaction to upward changes in spot prices than to downward changes in spot prices. This implies timing or pattern asymmetry. This asymmetry starts three days after the change in the spot price and lasts for four days.

  4. Inclined asymmetric librations in exterior resonances

    Science.gov (United States)

    Voyatzis, G.; Tsiganis, K.; Antoniadou, K. I.

    2018-04-01

    Librational motion in Celestial Mechanics is generally associated with the existence of stable resonant configurations and signified by the existence of stable periodic solutions and oscillation of critical (resonant) angles. When such an oscillation takes place around a value different than 0 or π , the libration is called asymmetric. In the context of the planar circular restricted three-body problem, asymmetric librations have been identified for the exterior mean motion resonances (MMRs) 1:2, 1:3, etc., as well as for co-orbital motion (1:1). In exterior MMRs the massless body is the outer one. In this paper, we study asymmetric librations in the three-dimensional space. We employ the computational approach of Markellos (Mon Not R Astron Soc 184:273-281, https://doi.org/10.1093/mnras/184.2.273, 1978) and compute families of asymmetric periodic orbits and their stability. Stable asymmetric periodic orbits are surrounded in phase space by domains of initial conditions which correspond to stable evolution and librating resonant angles. Our computations were focused on the spatial circular restricted three-body model of the Sun-Neptune-TNO system (TNO = trans-Neptunian object). We compare our results with numerical integrations of observed TNOs, which reveal that some of them perform 1:2 resonant, inclined asymmetric librations. For the stable 1:2 TNO librators, we find that their libration seems to be related to the vertically stable planar asymmetric orbits of our model, rather than the three-dimensional ones found in the present study.

  5. (Salen)Ti(Ⅳ)-Catalyzed Asymmetric Ring-opening of meso Epoxides Using Dithiophosphorus Acid as the Nucleophile

    Institute of Scientific and Technical Information of China (English)

    Zheng Hong ZHOU; Zhao Ming LI; Bing LIU; Kang Ying LI; Li Xin WANG; Guo Feng ZHAO; Qi Lin ZHOU; Chu Chi TANG

    2006-01-01

    The asymmetric ring-opening of epoxides with dithiophosphorus acids catalyzed by a (salen)Ti(Ⅳ) complex formed in situ from the reaction of Ti(OPr-i)4 and the chiral Schiff base derived from (1R,2R)-(+)-diaminocyclohexane was realized. The resulting products were obtained with low to good enantioselectivity (up to 73% ee).

  6. Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

    KAUST Repository

    Pluta, Roman

    2018-02-09

    A chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.

  7. Metal-Free Catalytic Asymmetric Fluorination of Keto Esters Using a Combination of Hydrogen Fluoride (HF) and Oxidant: Experiment and Computation

    KAUST Repository

    Pluta, Roman; Krach, Patricia E.; Cavallo, Luigi; Falivene, Laura; Rueping, Magnus

    2018-01-01

    A chiral iodoarene organocatalyst for the catalytic asymmetric fluorination has been developed. The catalyst was used in the asymmetric fluorination of carbonyl compounds, providing the products with a quaternary stereocenter with high enantioselectivities. Chiral hypervalent iodine difluoride intermediates were generated in situ by treatment of the catalyst with an oxidant and hydrogen fluoride as fluoride source. As such, the α-fluorination of a carbonyl compound was achieved with a nucleophilic fluorine source. A combined computational and experimental approach provided insight into the reaction mechanism and the origin of enantioselectivity.

  8. Asymmetric Synthesis of Optically Active Spirocyclic Indoline Scaffolds through an Enantioselective Reduction of Indoles

    KAUST Repository

    Borrmann, Ruediger

    2016-11-30

    An enantioselective synthesis of spirocyclic indoline scaffolds was achieved by applying an asymmetric iridium-catalyzed hydrogenation of 3H-indoles. Low catalyst loadings and mild reaction conditions provide a broad range of differently substituted products with excellent yields and enantioselectivities. The developed methodology allows an efficient synthesis of this important spirocyclic structural motif, which is present in numerous biologically active molecules and privileged structures in medicinal chemistry.

  9. Toxicity of Aromatic Ketone to Yeast Cell and Improvement of the Asymmetric Reduction of Aromatic Ketone Catalyzed by Yeast Cell with the Introduction of Resin Adsorption

    Directory of Open Access Journals (Sweden)

    Zhong-Hua Yang

    2008-01-01

    Full Text Available Asymmetric reduction of the prochiral aromatic ketone catalyzed by yeast cells is one of the most promising routes to produce its corresponding enantiopure aromatic alcohol, but the space-time yield does not meet people’s expectations. Therefore, the toxicity of aromatic ketone and aromatic alcohol to the yeast cell is investigated in this work. It has been found that the aromatic compounds are poisonous to the yeast cell. The activity of yeast cell decreases steeply when the concentration of acetophenone (ACP is higher than 30.0 mmol/L. Asymmetric reduction of acetophenone to chiral S-α-phenylethyl alcohol (PEA catalyzed by the yeast cell was chosen as the model reaction to study in detail the promotion effect of the introduction of the resin adsorption on the asymmetric reduction reaction. The resin acts as the substrate reservoir and product extraction agent in situ. It has been shown that this reaction could be remarkably improved with this technique when the appropriate kind of resin is applied. The enantioselectivity and yield are acceptable even though the initial ACP concentration reaches 72.2 mmol/L.

  10. Homologation Reaction of Ketones with Diazo Compounds.

    Science.gov (United States)

    Candeias, Nuno R; Paterna, Roberta; Gois, Pedro M P

    2016-03-09

    This review covers the addition of diazo compounds to ketones to afford homologated ketones, either in the presence or in the absence of promoters or catalysts. Reactions with diazoalkanes, aryldiazomethanes, trimethylsilyldiazomethane, α-diazo esters, and disubstituted diazo compounds are covered, commenting on the complex regiochemistry of the reaction and the nature of the catalysts and promoters. The recent reports on the enantioselective version of ketone homologation reactions are gathered in one section, followed by reports on the use of cyclic ketones ring expansion in total synthesis. Although the first reports of this reaction appeared in the literature almost one century ago, the recent achievements, in particular, for the asymmetric version, forecast the development of new breakthroughs in the synthetically valuable field of diazo chemistry.

  11. Pre-compound neutron evaporation in heavy ion fusion reactions

    International Nuclear Information System (INIS)

    Ajay Kumar; Singh, Hardev; Rajesh Kumar; Govil, I.M.; Golda, K.S.; Rakesh Kumar; Datta, S.K.; Yogi, B.K.; Viesti, G.

    2007-01-01

    In the present investigation, exclusive neutron spectra have been measured in coincidence with the observed γ-rays characteristic to the residual nuclei 53 Fe, 55 Fe and 56 Co. In this new experimental study, we have followed the strategy of forming the compound nucleus 58 Ni at the same excitation energy through two different entrance channels viz the mass symmetric reaction 31 P + 27 Al and the mass asymmetric reaction 12 C + 46 Ti

  12. Reversal modes in asymmetric Ni nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Leighton, B.; Pereira, A. [Departamento de Fisica, Universidad de Santiago de Chile (USACH), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Escrig, J., E-mail: jescrigm@gmail.com [Departamento de Fisica, Universidad de Santiago de Chile (USACH), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Center for the Development of Nanoscience and Nanotechnology (CEDENNA), Avda. Ecuador 3493, 917-0124 Santiago (Chile)

    2012-11-15

    We have investigated the evolution of the magnetization reversal mechanism in asymmetric Ni nanowires as a function of their geometry. Circular nanowires are found to reverse their magnetization by the propagation of a vortex domain wall, while in very asymmetric nanowires the reversal is driven by the propagation of a transverse domain wall. The effect of shape asymmetry of the wire on coercivity and remanence is also studied. Angular dependence of the remanence and coercivity is also addressed. Tailoring the magnetization reversal mechanism in asymmetric nanowires can be useful for magnetic logic and race-track memory, both of which are based on the displacement of magnetic domain walls. Finally, an alternative method to detect the presence of magnetic drops is proposed. - Highlights: Black-Right-Pointing-Pointer Asymmetry strongly modifies the magnetic behavior of a wire. Black-Right-Pointing-Pointer Very asymmetric nanowires reverse their magnetization by a transverse domain wall. Black-Right-Pointing-Pointer An alternative method to detect the presence of magnetic drops is proposed. Black-Right-Pointing-Pointer Tailoring the reversal mode in asymmetric nanowires can be useful for potential applications.

  13. Development of Ar-BINMOL-Derived Atropisomeric Ligands with Matched Axial and sp(3) Central Chirality for Catalytic Asymmetric Transformations.

    Science.gov (United States)

    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. Copyright © 2015 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Recent efforts directed to the development of more sustainable asymmetric organocatalysis.

    Science.gov (United States)

    Hernández, José G; Juaristi, Eusebio

    2012-06-04

    In line with the principles of "green" chemistry, organocatalysis seeks to reduce energy consumption and to optimize the use of the available resources, aiming to become a sustainable strategy in chemical transformations. Nevertheless, during the last decade diverse experimental protocols have made organocatalysis an even "greener" alternative by the use of friendlier reaction conditions, or via the application of solvent-free methodologies, or through the design and synthesis of more selective catalysts, or via the development of multicomponent one-pot organocatalytic reactions, or by the recycling and reuse of organocatalysts, or by means of the application of more energy-efficient activation techniques, among other approaches. In this feature article we review some of the remarkable advancements that have made it possible to develop even more sustainable asymmetric organocatalyzed methodologies.

  15. Asymmetric cryptography based on wavefront sensing.

    Science.gov (United States)

    Peng, Xiang; Wei, Hengzheng; Zhang, Peng

    2006-12-15

    A system of asymmetric cryptography based on wavefront sensing (ACWS) is proposed for the first time to our knowledge. One of the most significant features of the asymmetric cryptography is that a trapdoor one-way function is required and constructed by analogy to wavefront sensing, in which the public key may be derived from optical parameters, such as the wavelength or the focal length, while the private key may be obtained from a kind of regular point array. The ciphertext is generated by the encoded wavefront and represented with an irregular array. In such an ACWS system, the encryption key is not identical to the decryption key, which is another important feature of an asymmetric cryptographic system. The processes of asymmetric encryption and decryption are formulized mathematically and demonstrated with a set of numerical experiments.

  16. Quantifying social asymmetric structures.

    Science.gov (United States)

    Solanas, Antonio; Salafranca, Lluís; Riba, Carles; Sierra, Vicenta; Leiva, David

    2006-08-01

    Many social phenomena involve a set of dyadic relations among agents whose actions may be dependent. Although individualistic approaches have frequently been applied to analyze social processes, these are not generally concerned with dyadic relations, nor do they deal with dependency. This article describes a mathematical procedure for analyzing dyadic interactions in a social system. The proposed method consists mainly of decomposing asymmetric data into their symmetric and skew-symmetric parts. A quantification of skew symmetry for a social system can be obtained by dividing the norm of the skew-symmetric matrix by the norm of the asymmetric matrix. This calculation makes available to researchers a quantity related to the amount of dyadic reciprocity. With regard to agents, the procedure enables researchers to identify those whose behavior is asymmetric with respect to all agents. It is also possible to derive symmetric measurements among agents and to use multivariate statistical techniques.

  17. Very high intensity reaction chamber design

    International Nuclear Information System (INIS)

    Devaney, J.J.

    1975-09-01

    The problem of achieving very high intensity irradiation by light in minimal regions was studied. Three types of irradiation chamber are suggested: the common laser-reaction chamber, the folded concentric or near-concentric resonator, and the asymmetric confocal resonator. In all designs the ratio of high-intensity illuminated volume to other volume is highly dependent (to the 3 / 2 power) on the power and fluence tolerances of optical elements, primarily mirrors. Optimization of energy coupling is discussed for the common cavity. For the concentric cavities, optimization for both coherent and incoherent beams is treated. Formulae and numerical examples give the size of chambers, aspect ratios, maximum pass number, image sizes, fluences, and the like. Similarly for the asymmetric confocal chamber, formulae and numerical examples for fluences, dimensions, losses, and totally contained pass numbers are given

  18. Photocatalysis of irradiated semiconductor surfaces: Its application to water splitting and some organic reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sakata, T

    1985-05-01

    Hydrogen production from organic compounds and water was investigated using powdered semiconductor photocatalysts. The complete decomposition observed for several organic compounds demonstrated that water is involved in the reactions as an oxidizing agent. Photocatalyses of dyes and semiconductors were found to be applicable to amino acid synthesis. The quantum yields of photocatalytic amino acid synthesis using visible light are about 20%-40% in the absence of a metal catalyst such as platinum. Moreover the reactions are highly selective and depend strongly on the type of semiconductor. This method was applied to the asymmetric synthesis of amino acids using asymmetric catalysts. Rather high optical yields of 50% were achieved for the synthesis of L-phenylalanine.

  19. Asymmetric Catalysis with Organic Azides and Diazo Compounds Initiated by Photoinduced Electron Transfer.

    Science.gov (United States)

    Huang, Xiaoqiang; Webster, Richard D; Harms, Klaus; Meggers, Eric

    2016-09-28

    Electron-acceptor-substituted aryl azides and α-diazo carboxylic esters are used as substrates for visible-light-activated asymmetric α-amination and α-alkylation, respectively, of 2-acyl imidazoles catalyzed by a chiral-at-metal rhodium-based Lewis acid in combination with a photoredox sensitizer. This novel proton- and redox-neutral method provides yields of up to 99% and excellent enantioselectivities of up to >99% ee with broad functional group compatibility. Mechanistic investigations suggest that an intermediate rhodium enolate complex acts as a reductive quencher to initiate a radical process with the aryl azides and α-diazo carboxylic esters serving as precursors for nitrogen and carbon-centered radicals, respectively. This is the first report on using aryl azides and α-diazo carboxylic esters as substrates for asymmetric catalysis under photoredox conditions. These reagents have the advantage that molecular nitrogen is the leaving group and sole byproduct in this reaction.

  20. Palladium-catalyzed Asymmetric Hydrosilylation of Styrene and Its Derivatives with Chiral Phosphoramidite Ligands Containing Chiral Ferrocenyl Amine

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyun-Sub; Kim, Min Young; Ahn, Hyo Jin; Han, Jin Wook [Hanyang University, Seoul (Korea, Republic of)

    2016-06-15

    Asymmetric hydrosilylation was one of the most effective methods, which provided optically active organosilanes as a synthetically useful intermediate in organic synthesis. One useful transformation is the Tamao-Fleming oxidation, which is an oxidation reaction of carbon[BOND]silicone bond to afford optically active alcohols with retention of configuration. It is demonstrated that a palladium catalyst coordinating with phosphoramidite ligand (S {sub a},R {sub c},R {sub c,})-L3a from (S)-BINOL and chiral bis((R)-1-ferrocenylethyl) amine shows a high catalytic activity and enantioselectivity up to 97% ee in asymmetric hydrosilylation of styrene and its derivatives. The hydrosilylation of various olefin substrates using these ligands is in progress.

  1. Designing asymmetric multiferroics with strong magnetoelectric coupling

    Science.gov (United States)

    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.

  2. Modeling Electric Double-Layers Including Chemical Reaction Effects

    DEFF Research Database (Denmark)

    Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

    2014-01-01

    A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works...... for symmetric and asymmetric multi-species electrolytes and is not limited to a range of surface potentials. Numerical simulations are presented, for the case of a CaCO3 electrolyte solution in contact with a surface with rate-controlled protonation/deprotonation reactions. The surface charge and potential...... are determined by the surface reactions, and therefore they depends on the bulk solution composition and concentration...

  3. Chaos of several typical asymmetric systems

    International Nuclear Information System (INIS)

    Feng Jingjing; Zhang Qichang; Wang Wei

    2012-01-01

    The threshold for the onset of chaos in asymmetric nonlinear dynamic systems can be determined using an extended Padé method. In this paper, a double-well asymmetric potential system with damping under external periodic excitation is investigated, as well as an asymmetric triple-well potential system under external and parametric excitation. The integrals of Melnikov functions are established to demonstrate that the motion is chaotic. Threshold values are acquired when homoclinic and heteroclinic bifurcations occur. The results of analytical and numerical integration are compared to verify the effectiveness and feasibility of the analytical method.

  4. Congenital asymmetric crying face: a case report

    Directory of Open Access Journals (Sweden)

    Semra Kara

    2011-12-01

    Full Text Available Congenital asymmetric crying face is an anomalia caused by unilateral absence or weakness of depressor anguli oris muscle The major finding of the disease is the absence or weakness in the outer and lower movement of the commissure during crying. The other expression muscles are normal and the face is symmetric at rest. The asymmetry in congenital asymmetric crying face is most evident during infancy but decreases by age. Congenital asymmetric crying face can be associated with cervicofacial, musclebone, respiratory, genitourinary and central nervous system anomalia. It is diagnosed by physical examination. This paper presents a six days old infant with Congenital asymmetric crying face and discusses the case in terms of diagnosis and disease features.

  5. Asymmetric and nonlinear pass-through of crude oil prices to gasoline and natural gas prices

    International Nuclear Information System (INIS)

    Atil, Ahmed; Lahiani, Amine; Nguyen, Duc Khuong

    2014-01-01

    In this article, we use the recently developed nonlinear autoregressive distributed lags (NARDL) model to examine the pass-through of crude oil prices into gasoline and natural gas prices. Our approach allows us to simultaneously test the short- and long-run nonlinearities through positive and negative partial sum decompositions of the predetermined explanatory variables. It also offers the possibility to quantify the respective responses of gasoline and natural gas prices to positive and negative oil price shocks from the asymmetric dynamic multipliers. The obtained results indicate that oil prices affect gasoline prices and natural gas prices in an asymmetric and nonlinear manner, but the price transmission mechanism is not the same. Important policy implications can be learned from the empirical findings. - Highlights: • The pass-through of crude oil prices into gasoline and natural gas prices is examined. • We use a NARDL model to test for the long-run and short-run asymmetric reactions. • Both gasoline and natural gas prices significantly adjust to changes in the price of oil. • Negative oil shocks have greater effects than positive oil shocks. • Policy implications are discussed

  6. Recent developments in Cope-type hydroamination reactions of hydroxylamine and hydrazine derivatives.

    Science.gov (United States)

    Beauchemin, André M

    2013-11-07

    Cope-type hydroaminations are versatile for the direct amination of alkenes, alkynes and allenes using hydroxylamines and hydrazine derivatives. These reactions occur via a concerted, 5-membered cyclic transition state that is the microscopic reverse of the Cope elimination. This article focuses on recent developments, including intermolecular variants, directed reactions, and asymmetric variants using aldehydes as tethering catalysts, and their applications in target-oriented synthesis.

  7. Diverse lavas from closely spaced volcanoes drawing from a common parent: Emmons Lake Volcanic Center, Eastern Aleutian Arc

    Science.gov (United States)

    Mangan, M.; Miller, T.; Waythomas, C.; Trusdell, F.; Calvert, A.; Layer, P.

    2009-01-01

    Emmons Lake Volcanic Center (ELVC) on the lower Alaskan Peninsula is one of the largest and most diverse volcanic centers in the Aleutian Arc. Since the Middle Pleistocene, eruption of ~ 350 km3 of basalt through rhyolite has produced a 30 km, arc front chain of nested calderas and overlapping stratovolcanoes. ELVC has experienced as many as five major caldera-forming eruptions, the most recent, at ~ 27 ka, produced ~ 50 km3 of rhyolitic ignimbrite and ash fall. These violent silicic events were interspersed with less energetic, but prodigious, outpourings of basalt through dacite. Holocene eruptions are mostly basaltic andesite to andesite and historically recorded activity includes over 40 eruptions within the last 200 yr, all from Pavlof volcano, the most active site in the Aleutian Arc. Geochemical and geophysical observations suggest that although all ELVC eruptions derive from a common clinopyroxene + spinel + plagioclase fractionating high-aluminum basalt parent in the lower crust, magma follows one of two closely spaced, but distinct paths to the surface. Under the eastern end of the chain, magma moves rapidly and cleanly through a relatively young (~ 28 ka), hydraulically connected dike plexus. Steady supply, short magma residence times, and limited interaction with crustal rocks preserve the geochemistry of deep crustal processes. Below the western part of the chain, magma moves haltingly through a long-lived (~ 500 ka) and complex intrusive column in which many generations of basaltic to andesitic melts have mingled and fractionated. Buoyant, silicic melts periodically separate from the lower parts of the column to feed voluminous eruptions of dacite and rhyolite. Mafic lavas record a complicated passage through cumulate zones and hydrous silicic residues as manifested by disequilibrium phenocryst textures, incompatible element enrichments, and decoupling of REEs and HFSEs ratios. Such features are absent in mafic lavas from the younger part of the chain

  8. Non-Classical C–H···X Hydrogen Bonding and Its Role in Asymmetric Organocatalysis

    KAUST Repository

    Ajitha, Manjaly John; Huang, Kuo-Wei

    2016-01-01

    Non-classical hydrogen bonds (NCHBs) have attracted significant interest in the past decade particularly because of their important role in asymmetric catalytic systems. These weak interactions (< 4 kcal/mol) offer much flexibility1 Introduction2 Hydrogen Bonds (HBs) and Non-Classical Hydrogen Bonds (NCHBs)3 Early Developments in NCHBs4 Selected Examples of NCHBs in Organic Transformations5 Recent Examples of NCHBs in Enantioselective Reactions6 Conclusions and Outlook

  9. Dynamic JUNQ inclusion bodies are asymmetrically inherited in mammalian cell lines through the asymmetric partitioning of vimentin.

    Science.gov (United States)

    Ogrodnik, Mikołaj; Salmonowicz, Hanna; Brown, Rachel; Turkowska, Joanna; Średniawa, Władysław; Pattabiraman, Sundararaghavan; Amen, Triana; Abraham, Ayelet-chen; Eichler, Noam; Lyakhovetsky, Roman; Kaganovich, Daniel

    2014-06-03

    Aging is associated with the accumulation of several types of damage: in particular, damage to the proteome. Recent work points to a conserved replicative rejuvenation mechanism that works by preventing the inheritance of damaged and misfolded proteins by specific cells during division. Asymmetric inheritance of misfolded and aggregated proteins has been shown in bacteria and yeast, but relatively little evidence exists for a similar mechanism in mammalian cells. Here, we demonstrate, using long-term 4D imaging, that the vimentin intermediate filament establishes mitotic polarity in mammalian cell lines and mediates the asymmetric partitioning of damaged proteins. We show that mammalian JUNQ inclusion bodies containing soluble misfolded proteins are inherited asymmetrically, similarly to JUNQ quality-control inclusions observed in yeast. Mammalian IPOD-like inclusion bodies, meanwhile, are not always inherited by the same cell as the JUNQ. Our study suggests that the mammalian cytoskeleton and intermediate filaments provide the physical scaffold for asymmetric inheritance of dynamic quality-control JUNQ inclusions. Mammalian IPOD inclusions containing amyloidogenic proteins are not partitioned as effectively during mitosis as their counterparts in yeast. These findings provide a valuable mechanistic basis for studying the process of asymmetric inheritance in mammalian cells, including cells potentially undergoing polar divisions, such as differentiating stem cells and cancer cells.

  10. Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation

    Directory of Open Access Journals (Sweden)

    Wei Jie Li

    2010-03-01

    Full Text Available Seven polyoxazoline ligands were synthesized in high yield in a one-pot reaction by heating polycarboxylic acids or their esters and chiral β-amino alcohols under reflux with concomitant removal of water or the alcohol produced in the reaction. The method is much simpler and more efficient in comparison to those methods reported in the literature.The compounds were used as chiral ligands in the rhodium-catalyzed asymmetric hydrosilylation of aromatic ketones, and the effects of the linkers and the substituents present on the oxazoline rings on the yield and enantioselectivity investigated. Compound 2 was identified as the best ligand of this family for the hydrosilylation of aromatic ketones.

  11. Comparison of different proximity potentials for asymmetric colliding nuclei

    International Nuclear Information System (INIS)

    Dutt, Ishwar; Puri, Rajeev K.

    2010-01-01

    Using the different versions of phenomenological proximity potential as well as other parametrizations within the proximity concept, we perform a detailed comparative study of fusion barriers for asymmetric colliding nuclei with asymmetry parameter as high as 0.23. In all, 12 different proximity potentials are robust against the experimental data of 60 reactions. Our detailed study reveals that the surface energy coefficient as well as radius of the colliding nuclei depend significantly on the asymmetry parameter. All models are able to explain the fusion barrier heights within ±10% on the average. The potentials due to Bass 80, AW 95, and Denisov DP explain nicely the fusion cross sections at above- as well as below-barrier energies.

  12. Systematic studies using 2-(1-adamantylethynyl)pyrimidine-5-carbaldehyde as a starting material in Soai's asymmetric autocatalysis.

    Science.gov (United States)

    Busch, Mark; Schlageter, Martin; Weingand, Daniel; Gehring, Timo

    2009-08-17

    Herein, we present a new substrate for the Soai reaction, which has an adamantylethynyl residue (1 g) and exhibits asymmetric autocatalysis, yielding products with enantiomeric excesses above 99%. For the first time, all reactions were performed on a parallel synthesizer system to ensure identical reaction conditions. A detailed systematic study of reaction parameters was performed and we report the highest enhancements of enantiomeric excess reported so far in the Soai reaction in one reaction cycle (7.2-->94.1% ee or 3.1-->92.1% ee). Our results led to a set of reaction parameters that yield reproducible results. Therefore, our new starting material 1 g is suitable for systematic and mechanistic studies on this remarkable reaction. A series of experiments designed to quantify the amplification of enantiomeric excess demonstrated that the reaction can be used in principle as a tool for the detection of low enantiomeric excesses: under definite conditions, an unknown low enantiomeric excess (0.1-7%) was amplified to a detectable one. A back calculation to the original value offers a new method for the determination of small enantiomeric excesses.

  13. Rapid Asymmetric Synthesis of Disubstituted Allenes by Coupling of Flow-Generated Diazo Compounds and Propargylated Amines.

    Science.gov (United States)

    Poh, Jian-Siang; Makai, Szabolcs; von Keutz, Timo; Tran, Duc N; Battilocchio, Claudio; Pasau, Patrick; Ley, Steven V

    2017-02-06

    We report herein the asymmetric coupling of flow-generated unstabilized diazo compounds and propargylated amine derivatives, using a new pyridinebis(imidazoline) ligand, a copper catalyst and base. The reaction proceeds rapidly, generating chiral allenes in 10-20 minutes with high enantioselectivity (89-98 % de/ee), moderate yields and a wide functional group tolerance. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Pericyclic reactions in an aqueous molecular flask.

    Science.gov (United States)

    Murase, Takashi; Fujita, Makoto

    2010-10-01

    A self-assembled molecular flask with a nanometer-sized restricted cavity offers a new reaction environment that is quite different from the bulk solution. The self-assembled cage accommodates a pair of hydrophobic molecules to perform unusual Diels-Alder reactions and [2+2] photoadditions of otherwise unreactive aromatic molecules. In this cage, for example, the Diels-Alder reaction of naphthalene proceeds smoothly under mild conditions, and aceanthrylene shows reactivity for both [2+2] and [2+4] cycloadditions via the identical ternary host-guest complex. The observed greatly enhanced reactivity stems from the increased local concentration and pre-organization of the substrate pair within the cage, which reduces the entropic cost and switches the reaction profile from a bimolecular to a pseudo-intramolecular reaction pathway. The reinforced orientation and arrangement of substrate pairs specify regio- and stereo-selectivities of the subsequent reactions in the cavity. Chiral auxiliaries outside the cage create the inner chiral environment and induce asymmetric reactions inside the cage (up to 50% ee). © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

  15. Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

    Directory of Open Access Journals (Sweden)

    Katherine M. Byrd

    2015-04-01

    Full Text Available The conjugate addition reaction has been a useful tool in the formation of carbon–carbon bonds. The utility of this reaction has been demonstrated in the synthesis of many natural products, materials, and pharmacological agents. In the last three decades, there has been a significant increase in the development of asymmetric variants of this reaction. Unfortunately, conjugate addition reactions using α,β-unsaturated amides and lactams remain underdeveloped due to their inherently low reactivity. This review highlights the work that has been done on both diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams.

  16. Study of asymmetric fission yield behavior from neutron-deficient Hg isotope

    International Nuclear Information System (INIS)

    Perkasa, Y. S.; Waris, A.; Kurniadi, R.; Su'ud, Z.

    2014-01-01

    A study of asymmetric fission yield behavior from a neutron-deficient Hg isotope has been conducted. The fission yield calculation of the neutron-deficient Hg isotope using Brownian Metropolis shape had showed unusual result at decreasing energy. In this paper, this interesting feature will be validated by using nine degree of scission shapes parameterization from Brosa model that had been implemented in TALYS nuclear reaction code. This validation is intended to show agreement between both model and the experiment result. The expected result from these models considered to be different due to dynamical properties that implemented in both models

  17. Delay-induced wave instabilities in single-species reaction-diffusion systems

    Science.gov (United States)

    Otto, Andereas; Wang, Jian; Radons, Günter

    2017-11-01

    The Turing (wave) instability is only possible in reaction-diffusion systems with more than one (two) components. Motivated by the fact that a time delay increases the dimension of a system, we investigate the presence of diffusion-driven instabilities in single-species reaction-diffusion systems with delay. The stability of arbitrary one-component systems with a single discrete delay, with distributed delay, or with a variable delay is systematically analyzed. We show that a wave instability can appear from an equilibrium of single-species reaction-diffusion systems with fluctuating or distributed delay, which is not possible in similar systems with constant discrete delay or without delay. More precisely, we show by basic analytic arguments and by numerical simulations that fast asymmetric delay fluctuations or asymmetrically distributed delays can lead to wave instabilities in these systems. Examples, for the resulting traveling waves are shown for a Fisher-KPP equation with distributed delay in the reaction term. In addition, we have studied diffusion-induced instabilities from homogeneous periodic orbits in the same systems with variable delay, where the homogeneous periodic orbits are attracting resonant periodic solutions of the system without diffusion, i.e., periodic orbits of the Hutchinson equation with time-varying delay. If diffusion is introduced, standing waves can emerge whose temporal period is equal to the period of the variable delay.

  18. Asymmetric Brønsted Acid Catalyzed Substitution of Diaryl Methanols with Thiols and Alcohols for the Synthesis of Chiral Thioethers and Ethers

    KAUST Repository

    Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Mader, Steffen; Sako, Makoto; Sasai, Hiroaki; Atodiresei, Iuliana; Rueping, Magnus

    2016-01-01

    An enantioselective addition of thiols and alcohols to aza-ortho-quinone methides, starting from diaryl methanols, was developed. The asymmetric additions occur under mild reaction conditions in the presence of chiral phosphoric acids and furnish the corresponding adducts with excellent yields and enantioselectivities.

  19. Asymmetric Brønsted Acid Catalyzed Substitution of Diaryl Methanols with Thiols and Alcohols for the Synthesis of Chiral Thioethers and Ethers

    KAUST Repository

    Chatupheeraphat, Adisak

    2016-03-08

    An enantioselective addition of thiols and alcohols to aza-ortho-quinone methides, starting from diaryl methanols, was developed. The asymmetric additions occur under mild reaction conditions in the presence of chiral phosphoric acids and furnish the corresponding adducts with excellent yields and enantioselectivities.

  20. The regio- and stereospecific synthesis of diarylpropenyllithium compounds from dimethylamino- and dimethylaminomethyl-substituted diarylacetylenes viatransmetallation reactions involving diarylpropenylmagnesium and tin compounds

    NARCIS (Netherlands)

    Koten, G. van; Hoedt, R.W.M. ten; Noltes, J.G.

    1979-01-01

    Dimethylamino- and dimethylaminomethyl-substituted diarylacetylenes were prepared by the Pd(PPh{3}){4}-catalyzed coupling reaction of dimethylamino- and dimethylaminomethyl-substituted aryl halides with arylacetylenes.Reaction of the asymmetric diarylacetylenes with methylmagnesium bromide in the

  1. Synthesis and optical properties of novel asymmetric perylene bisimides

    International Nuclear Information System (INIS)

    Tsai, Hsing-Yang; Chen, Kew-Yu

    2014-01-01

    A novel series of asymmetric perylene bisimides, 1-amino-7-nitroperylene bisimides (1a–1c), was synthesized and fully characterized. These molecules undergo an excited-state intramolecular electron transfer reaction, resulting in a unique charge transfer emission in the near-infrared region, of which the peak wavelength exhibits strong solvatochromism. The dipole moments of these compounds have been estimated using the Lippert–Mataga equation, and upon excitation, the molecules show larger dipole moment changes than those of the symmetric 1,7-diaminoperylene bisimides (2a–2c). Furthermore, these dyes undergo two quasi-reversible one-electron oxidations and two quasi-reversible one-electron reductions in dichloromethane at modest potentials. They display good thermal stability and optical stability that can be used as stable near-infrared fluorescent dyes. Their spectroscopic properties in various conditions and complementary time-dependent density functional theory calculations are reported. - Highlights: • 1-amino-7-nitroperylene bisimide dyes were synthesized. • These molecules undergo an excited-state intramolecular electron transfer reaction. • They can be used as stable near-infrared fluorescent dyes

  2. Renewable resource management under asymmetric information

    DEFF Research Database (Denmark)

    Jensen, Frank; Andersen, Peder; Nielsen, Max

    2013-01-01

    Asymmetric information between fishermen and the regulator is important within fisheries. The regulator may have less information about stock sizes, prices, costs, effort, productivity and catches than fishermen. With asymmetric information, a strong analytical tool is principal-agent analysis....... In this paper, we study asymmetric information about productivity within a principal-agent framework and a tax on fishing effort is considered. It is shown that a second best optimum can be achieved if the effort tax is designed such that low-productivity agents rent is exhausted, while high-productivity agents...... receive an information rent. The information rent is equivalent to the total incentive cost. The incentive costs arise as we want to reveal the agent's type....

  3. Subcopula-based measure of asymmetric association for contingency tables.

    Science.gov (United States)

    Wei, Zheng; Kim, Daeyoung

    2017-10-30

    For the analysis of a two-way contingency table, a new asymmetric association measure is developed. The proposed method uses the subcopula-based regression between the discrete variables to measure the asymmetric predictive powers of the variables of interest. Unlike the existing measures of asymmetric association, the subcopula-based measure is insensitive to the number of categories in a variable, and thus, the magnitude of the proposed measure can be interpreted as the degree of asymmetric association in the contingency table. The theoretical properties of the proposed subcopula-based asymmetric association measure are investigated. We illustrate the performance and advantages of the proposed measure using simulation studies and real data examples. Copyright © 2017 John Wiley & Sons, Ltd.

  4. Modelling asymmetric growth in crowded plant communities

    DEFF Research Database (Denmark)

    Damgaard, Christian

    2010-01-01

    A class of models that may be used to quantify the effect of size-asymmetric competition in crowded plant communities by estimating a community specific degree of size-asymmetric growth for each species in the community is suggested. The model consists of two parts: an individual size......-asymmetric growth part, where growth is assumed to be proportional to a power function of the size of the individual, and a term that reduces the relative growth rate as a decreasing function of the individual plant size and the competitive interactions from other plants in the neighbourhood....

  5. Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

    KAUST Repository

    Wang, Tianli

    2015-06-02

    Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.

  6. Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

    KAUST Repository

    Wang, Tianli; Yu, Zhaoyuan; Hoon, Ding Long; Huang, Kuo-Wei; Lan, Yu; Lu, Yixin

    2015-01-01

    Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.

  7. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    -molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...... and asymmetric charge transfer reactions between several first-row transition metals in water. The results are compared to experiments and rationalised with classical analytic expressions. Shortcomings of the methods are accounted for with clear steps towards improved accuracy. Later the analysis is extended...

  8. Asymmetric dominance and asymmetric mate choice oppose premating isolation after allopatric divergence.

    Science.gov (United States)

    Sefc, Kristina M; Hermann, Caroline M; Steinwender, Bernd; Brindl, Hanna; Zimmermann, Holger; Mattersdorfer, Karin; Postl, Lisbeth; Makasa, Lawrence; Sturmbauer, Christian; Koblmüller, Stephan

    2015-04-01

    Assortative mating promotes reproductive isolation and allows allopatric speciation processes to continue in secondary contact. As mating patterns are determined by mate preferences and intrasexual competition, we investigated male-male competition and behavioral isolation in simulated secondary contact among allopatric populations. Three allopatric color morphs of the cichlid fish Tropheus were tested against each other. Dyadic male-male contests revealed dominance of red males over bluish and yellow-blotch males. Reproductive isolation in the presence of male-male competition was assessed from genetic parentage in experimental ponds and was highly asymmetric among pairs of color morphs. Red females mated only with red males, whereas the other females performed variable degrees of heteromorphic mating. Discrepancies between mating patterns in ponds and female preferences in a competition-free, two-way choice paradigm suggested that the dominance of red males interfered with positive assortative mating of females of the subordinate morphs and provoked asymmetric hybridization. Between the nonred morphs, a significant excess of negative assortative mating by yellow-blotch females with bluish males did not coincide with asymmetric dominance among males. Hence, both negative assortative mating preferences and interference of male-male competition with positive assortative preferences forestall premating isolation, the latter especially in environments unsupportive of competition-driven spatial segregation.

  9. Method development of damage detection in asymmetric buildings

    Science.gov (United States)

    Wang, Yi; Thambiratnam, David P.; Chan, Tommy H. T.; Nguyen, Andy

    2018-01-01

    Aesthetics and functionality requirements have caused most buildings to be asymmetric in recent times. Such buildings exhibit complex vibration characteristics under dynamic loads as there is coupling between the lateral and torsional components of vibration, and are referred to as torsionally coupled buildings. These buildings require three dimensional modelling and analysis. In spite of much recent research and some successful applications of vibration based damage detection methods to civil structures in recent years, the applications to asymmetric buildings has been a challenging task for structural engineers. There has been relatively little research on detecting and locating damage specific to torsionally coupled asymmetric buildings. This paper aims to compare the difference in vibration behaviour between symmetric and asymmetric buildings and then use the vibration characteristics for predicting damage in them. The need for developing a special method to detect damage in asymmetric buildings thus becomes evident. Towards this end, this paper modifies the traditional modal strain energy based damage index by decomposing the mode shapes into their lateral and vertical components and to form component specific damage indices. The improved approach is then developed by combining the modified strain energy based damage indices with the modal flexibility method which was modified to suit three dimensional structures to form a new damage indicator. The procedure is illustrated through numerical studies conducted on three dimensional five-story symmetric and asymmetric frame structures with the same layout, after validating the modelling techniques through experimental testing of a laboratory scale asymmetric building model. Vibration parameters obtained from finite element analysis of the intact and damaged building models are then applied into the proposed algorithms for detecting and locating the single and multiple damages in these buildings. The results

  10. Catalytic asymmetric Meerwein-Ponndorf-Verley reduction of glyoxylates induced by a chiral N,N'-dioxide/Y(OTf)3 complex.

    Science.gov (United States)

    Wu, Wangbin; Zou, Sijia; Lin, Lili; Ji, Jie; Zhang, Yuheng; Ma, Baiwei; Liu, Xiaohua; Feng, Xiaoming

    2017-03-18

    An asymmetric Meerwein-Ponndorf-Verley (MPV) reduction of glyoxylates was for the first time accomplished via an N,N'-dioxide/Y(OTf) 3 complex with aluminium alkoxide and molecular sieves (MSs) as crucial additives. A variety of optically active α-hydroxyesters were obtained with excellent results. A possible reaction mechanism was proposed based on the experiments.

  11. High-Throughput Assay for Enantiomeric Excess Determination in 1,2- and 1,3-Diols and Direct Asymmetric Reaction Screening.

    Science.gov (United States)

    Shcherbakova, Elena G; Brega, Valentina; Lynch, Vincent M; James, Tony D; Anzenbacher, Pavel

    2017-07-26

    A simple and efficient method for determination of the yield, enantiomeric/diasteriomeric excess (ee/de), and absolute configuration of crude chiral diols without the need of work-up and product isolation in a high throughput setting is described. This approach utilizes a self-assembled iminoboronate ester formed as a product by dynamic covalent self-assembly of a chiral diol with an enantiopure fluorescent amine such as tryptophan methyl ester or tryptophanol and 2-formylphenylboronic acid. The resulting diastereomeric boronates display different photophysical properties and allow for fluorescence-based ee determination of molecules containing a 1,2- or 1,3-diol moiety. This method has been utilized for the screening of ee in a number of chiral diols including atorvastatin, a statin used for the treatment of hypercholesterolemia. Noyori asymmetric hydrogenation of benzil was performed in a highly parallel fashion with errors products from the parallel asymmetric synthesis in real time and in a high-throughput screening (HTS) fashion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Asymmetric Synthesis via Chiral Aziridines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Harden, Adrian; Wyatt, Paul

    1996-01-01

    A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines)]. In the b......A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines...

  13. Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies.

    Science.gov (United States)

    Bardhan, Jaydeep P; Jungwirth, Pavel; Makowski, Lee

    2012-09-28

    Two mechanisms have been proposed to drive asymmetric solvent response to a solute charge: a static potential contribution similar to the liquid-vapor potential, and a steric contribution associated with a water molecule's structure and charge distribution. In this work, we use free-energy perturbation molecular-dynamics calculations in explicit water to show that these mechanisms act in complementary regimes; the large static potential (∼44 kJ/mol/e) dominates asymmetric response for deeply buried charges, and the steric contribution dominates for charges near the solute-solvent interface. Therefore, both mechanisms must be included in order to fully account for asymmetric solvation in general. Our calculations suggest that the steric contribution leads to a remarkable deviation from the popular "linear response" model in which the reaction potential changes linearly as a function of charge. In fact, the potential varies in a piecewise-linear fashion, i.e., with different proportionality constants depending on the sign of the charge. This discrepancy is significant even when the charge is completely buried, and holds for solutes larger than single atoms. Together, these mechanisms suggest that implicit-solvent models can be improved using a combination of affine response (an offset due to the static potential) and piecewise-linear response (due to the steric contribution).

  14. Affine-response model of molecular solvation of ions: Accurate predictions of asymmetric charging free energies

    Science.gov (United States)

    Bardhan, Jaydeep P.; Jungwirth, Pavel; Makowski, Lee

    2012-01-01

    Two mechanisms have been proposed to drive asymmetric solvent response to a solute charge: a static potential contribution similar to the liquid-vapor potential, and a steric contribution associated with a water molecule's structure and charge distribution. In this work, we use free-energy perturbation molecular-dynamics calculations in explicit water to show that these mechanisms act in complementary regimes; the large static potential (∼44 kJ/mol/e) dominates asymmetric response for deeply buried charges, and the steric contribution dominates for charges near the solute-solvent interface. Therefore, both mechanisms must be included in order to fully account for asymmetric solvation in general. Our calculations suggest that the steric contribution leads to a remarkable deviation from the popular “linear response” model in which the reaction potential changes linearly as a function of charge. In fact, the potential varies in a piecewise-linear fashion, i.e., with different proportionality constants depending on the sign of the charge. This discrepancy is significant even when the charge is completely buried, and holds for solutes larger than single atoms. Together, these mechanisms suggest that implicit-solvent models can be improved using a combination of affine response (an offset due to the static potential) and piecewise-linear response (due to the steric contribution). PMID:23020318

  15. Optimal multicopy asymmetric Gaussian cloning of coherent states

    International Nuclear Information System (INIS)

    Fiurasek, Jaromir; Cerf, Nicolas J.

    2007-01-01

    We investigate the asymmetric Gaussian cloning of coherent states which produces M copies from N input replicas in such a way that the fidelity of each copy may be different. We show that the optimal asymmetric Gaussian cloning can be performed with a single phase-insensitive amplifier and an array of beam splitters. We obtain a simple analytical expression characterizing the set of optimal asymmetric Gaussian cloning machines and prove the optimality of these cloners using the formalism of Gaussian completely positive maps and semidefinite programming techniques. We also present an alternative implementation of the asymmetric cloning machine where the phase-insensitive amplifier is replaced with a beam splitter, heterodyne detector, and feedforward

  16. Optimal multicopy asymmetric Gaussian cloning of coherent states

    Science.gov (United States)

    Fiurášek, Jaromír; Cerf, Nicolas J.

    2007-05-01

    We investigate the asymmetric Gaussian cloning of coherent states which produces M copies from N input replicas in such a way that the fidelity of each copy may be different. We show that the optimal asymmetric Gaussian cloning can be performed with a single phase-insensitive amplifier and an array of beam splitters. We obtain a simple analytical expression characterizing the set of optimal asymmetric Gaussian cloning machines and prove the optimality of these cloners using the formalism of Gaussian completely positive maps and semidefinite programming techniques. We also present an alternative implementation of the asymmetric cloning machine where the phase-insensitive amplifier is replaced with a beam splitter, heterodyne detector, and feedforward.

  17. Two-proton transfer reactions on even Ni and Zn isotopes

    International Nuclear Information System (INIS)

    Boucenna, A.; Kraus, L.; Linck, I.; Tsan Ung Chan

    1988-01-01

    Two-proton transfer reactions induced by 112 MeV 12 C ions on even Ni and Zn isotopes are found to be less selective than the analogous two-neutron transfer reactions induced on the same targets in a similar incident energy range. The additional collective aspects observed in the proton transfer are examined in view of a semiphenomenological model of two quasi-particles coupled to a triaxial asymmetric rotor. Tentative spin and parity assignments emerge from this comparison, from crude shell model calculations and from systematic trends

  18. Organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds

    International Nuclear Information System (INIS)

    Maltsev, O V; Beletskaya, Irina P; Zlotin, Sergei G

    2011-01-01

    Recent applications of organocatalytic Michael and Friedel–Crafts reactions in enantioselective synthesis of biologically active compounds: natural products, pharmaceutical agents and plant protection agents are reviewed. The key mechanisms of stereoinduction, types of organocatalysts and reagents used in these reactions are considered. The material is classified according to the type of newly formed bonds incorporating the asymmetric carbon atom, and the information for the most numerous C–C coupling reactions is systematized according to the natures of the electrophile and the nucleophile. The bibliography includes 433 references.

  19. Likelihood for transcriptions in a genetic regulatory system under asymmetric stable Lévy noise.

    Science.gov (United States)

    Wang, Hui; Cheng, Xiujun; Duan, Jinqiao; Kurths, Jürgen; Li, Xiaofan

    2018-01-01

    This work is devoted to investigating the evolution of concentration in a genetic regulation system, when the synthesis reaction rate is under additive and multiplicative asymmetric stable Lévy fluctuations. By focusing on the impact of skewness (i.e., non-symmetry) in the probability distributions of noise, we find that via examining the mean first exit time (MFET) and the first escape probability (FEP), the asymmetric fluctuations, interacting with nonlinearity in the system, lead to peculiar likelihood for transcription. This includes, in the additive noise case, realizing higher likelihood of transcription for larger positive skewness (i.e., asymmetry) index β, causing a stochastic bifurcation at the non-Gaussianity index value α = 1 (i.e., it is a separating point or line for the likelihood for transcription), and achieving a turning point at the threshold value β≈-0.5 (i.e., beyond which the likelihood for transcription suddenly reversed for α values). The stochastic bifurcation and turning point phenomena do not occur in the symmetric noise case (β = 0). While in the multiplicative noise case, non-Gaussianity index value α = 1 is a separating point or line for both the MFET and the FEP. We also investigate the noise enhanced stability phenomenon. Additionally, we are able to specify the regions in the whole parameter space for the asymmetric noise, in which we attain desired likelihood for transcription. We have conducted a series of numerical experiments in "regulating" the likelihood of gene transcription by tuning asymmetric stable Lévy noise indexes. This work offers insights for possible ways of achieving gene regulation in experimental research.

  20. Survey of beta-particle interaction experiments with asymmetric matter

    Science.gov (United States)

    Van Horn, J. David; Wu, Fei

    2018-05-01

    Asymmetry is a basic property found at multiple scales in the universe. Asymmetric molecular interactions are fundamental to the operation of biological systems in both signaling and structural roles. Other aspects of asymmetry are observed and useful in many areas of science and engineering, and have been studied since the discovery of chirality in tartrate salts. The observation of parity violation in beta decay provided some impetus for later experiments using asymmetric particles. Here we survey historical work and experiments related to electron (e-) or positron (e+) polarimetry and their interactions with asymmetric materials in gas, liquid and solid forms. Asymmetric interactions may be classified as: 1) stereorecognition, 2) stereoselection and 3) stereoinduction. These three facets of physical stereochemistry are unique but interrelated; and examples from chemistry and materials science illustrate these aspects. Experimental positron and electron interactions with asymmetric materials may be classified in like manner. Thus, a qualitative assessment of helical and polarized positron experiments with different forms of asymmetric matter from the past 40 years is presented, as well as recent experiments with left-hand and right-hand single crystal quartz and organic compounds. The purpose of this classification and review is to evaluate the field for potential new experiments and directions for positron (or electron) studies with asymmetric materials.

  1. Efficient Asymmetric Synthesis of S,S-2-methylsulfanyl-2-methylsulfinyl-1-indanone

    Directory of Open Access Journals (Sweden)

    Derisvaldo Rosa Paiva

    2013-05-01

    Full Text Available Diastereoselective synthesis of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanol by reduction of SS-2-methylsulfanyl-2-methylsulfinyl-1-indanone optically enriched demonstrating to be highly efficiency using the sulfanyl group as asymmetric induction control agent during an addition reaction to carbonyl group.The 2-methylsulfinyl-1-indanone was obtained for the first time in one unique step without further oxidation steps. The synthesis of SR, SS of 2-methylsulphinyl-1-indanone optically enriched in good yield and good enantiomeric excess determined by nuclear magnetic resonance technique employing the Kagan reagent as chiral shift agent.

  2. Studies toward the asymmetric synthesis of the right part of the mycalamides.

    Science.gov (United States)

    Zhong, H Marlon; Sohn, Jeong-Hun; Rawal, Viresh H

    2007-01-19

    Described herein is the asymmetric synthesis of a functionalized, trioxadecalin unit that comprises the right-hand part of the mycalamides and related natural products. The synthetic route involves a 16-step sequence that accomplishes the formation of two heterocyclic rings and the generation of five stereocenters. The synthesis commenced with a C2-symmetric starting material, diethyl D-tartrate, and took advantage of a relay of diastereoselective reactions to extend this four-carbon chain and introduce new chiral centers. Subsequent electrophile-mediated cyclization afforded the desired pyran ring, which was then transformed into the desired, functionalized trioxadecalin skeleton.

  3. NeoPHOX – a structurally tunable ligand system for asymmetric catalysis

    Directory of Open Access Journals (Sweden)

    Jaroslav Padevět

    2016-06-01

    Full Text Available A synthesis of new NeoPHOX ligands derived from serine or threonine has been developed. The central intermediate is a NeoPHOX derivative bearing a methoxycarbonyl group at the stereogenic center next to the oxazoline N atom. The addition of methylmagnesium chloride leads to a tertiary alcohol, which can be acylated or silylated to produce NeoPHOX ligands with different sterical demand. The new NeoPHOX ligands were tested in the iridium-catalyzed asymmetric hydrogenation and palladium-catalyzed allylic substitution. In both reactions high enantioselectivities were achieved, that were comparable to the enantioselectivities obtained with the up to now best NeoPHOX ligand derived from expensive tert-leucine.

  4. Modelling the monetary policy reaction function of the Colombian Central Bank

    OpenAIRE

    Otero, Jesus; Ramírez, Manuel

    2008-01-01

    This paper proposes a simple Ordered Probit model to analyse the monetary policy reaction function of the Colombian Central Bank. There is evidence that the reaction function is asymmetric, in the sense that the Bank increases the Bank rate when the gap between observed inflation and the inflation target (lagged once) is positive, but it does not reduce the Bank rate when the gap is negative. This behaviour suggests that the Bank is more interested in fulfilling the announced inflation target...

  5. A Pyrene-Linked Cavity within a β-Barrel Protein Promotes an Asymmetric Diels-Alder Reaction.

    Science.gov (United States)

    Himiyama, Tomoki; Taniguchi, Naomasa; Kato, Shunsuke; Onoda, Akira; Hayashi, Takashi

    2017-10-23

    A unique π-expanded reaction cavity tethering a polycyclic moiety which provides a platform for substrate binding was constructed within the robust β-barrel structure of nitrobindin (NB). NB variants with cavities of different sizes and shapes are coupled with N-(1-pyrenyl)maleimide (Pyr) to prepare a series of NB-Pyr conjugates. The orientation of the pyrene moiety is fixed within the cavity by the coupling reaction. The fluorescent quenching analysis of NB-Pyr indicates that azachalcone (aza), which is a dienophile for a Diels-Alder (DA) reaction, is efficiently incorporated within the pyrene-linked reaction cavity by the aromatic interaction. The DA reaction between aza and cyclopentadiene proceeds within the reaction cavity of NB-Pyr in the presence of Cu II ion in high yield and high enantio- and regioselectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Construction of axial chirality by rhodium-catalyzed asymmetric dehydrogenative Heck coupling of biaryl compounds with alkenes.

    Science.gov (United States)

    Zheng, Jun; You, Shu-Li

    2014-11-24

    Enantioselective construction of axially chiral biaryls by direct C-H bond functionalization reactions has been realized. Novel axially chiral biaryls were synthesized by the direct C-H bond olefination of biaryl compounds, using a chiral [Cp*Rh(III)] catalyst, in good to excellent yields and enantioselectivities. The obtained axially chiral biaryls were found as suitable ligands for rhodium-catalyzed asymmetric conjugate additions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Time-Dependent-Asymmetric-Linear-Parsimonious Ancestral State Reconstruction.

    Science.gov (United States)

    Didier, Gilles

    2017-10-01

    The time-dependent-asymmetric-linear parsimony is an ancestral state reconstruction method which extends the standard linear parsimony (a.k.a. Wagner parsimony) approach by taking into account both branch lengths and asymmetric evolutionary costs for reconstructing quantitative characters (asymmetric costs amount to assuming an evolutionary trend toward the direction with the lowest cost). A formal study of the influence of the asymmetry parameter shows that the time-dependent-asymmetric-linear parsimony infers states which are all taken among the known states, except for some degenerate cases corresponding to special values of the asymmetry parameter. This remarkable property holds in particular for the Wagner parsimony. This study leads to a polynomial algorithm which determines, and provides a compact representation of, the parametric reconstruction of a phylogenetic tree, that is for all the unknown nodes, the set of all the possible reconstructed states associated with the asymmetry parameters leading to them. The time-dependent-asymmetric-linear parsimony is finally illustrated with the parametric reconstruction of the body size of cetaceans.

  8. Evolution of magnetization due to asymmetric dimerization: theoretical considerations and application to aberrant oligomers formed by apoSOD1(2SH).

    Science.gov (United States)

    Sekhar, Ashok; Bain, Alex D; Rumfeldt, Jessica A O; Meiering, Elizabeth M; Kay, Lewis E

    2016-02-17

    A set of coupled differential equations is presented describing the evolution of magnetization due to an exchange reaction whereby a pair of identical monomers form an asymmetric dimer. In their most general form the equations describe a three-site exchange process that reduces to two-site exchange under certain limiting conditions that are discussed. An application to the study of sparsely populated, transiently formed sets of aberrant dimers, symmetric and asymmetric, of superoxide dismutase is presented. Fits of concentration dependent CPMG relaxation dispersion profiles provide measures of the dimer dissociation constants and both on- and off-rates. Dissociation constants on the order of 70 mM are extracted from fits of the data, with dimeric populations of ∼2% and lifetimes of ∼6 and ∼2 ms for the symmetric and asymmetric complexes, respectively. This work emphasizes the important role that NMR relaxation experiments can play in characterizing very weak molecular complexes that remain invisible to most biophysical approaches.

  9. How asymmetrical task dependence and task interdependence interact:an individual level study into the effects on affective reactions

    OpenAIRE

    Jong, Simon B. De; Bal, P. Matthijs

    2014-01-01

    Purpose – This study investigates whether research and practice on task design and work teams could benefit from a more nuanced perspective on task (inter)dependencies among team members. Prior research often overlooked that task interdependence captures the average exchange of resources, while asymmetrical task dependence captures the inequalities within an individual's work relationships. To date, no study on work teams has combined the two aspects. Design/methodology/approach – Data was ob...

  10. Asymmetric strand segregation: epigenetic costs of genetic fidelity?

    Directory of Open Access Journals (Sweden)

    Diane P Genereux

    2009-06-01

    Full Text Available Asymmetric strand segregation has been proposed as a mechanism to minimize effective mutation rates in epithelial tissues. Under asymmetric strand segregation, the double-stranded molecule that contains the oldest DNA strand is preferentially targeted to the somatic stem cell after each round of DNA replication. This oldest DNA strand is expected to have fewer errors than younger strands because some of the errors that arise on daughter strands during their synthesis fail to be repaired. Empirical findings suggest the possibility of asymmetric strand segregation in a subset of mammalian cell lineages, indicating that it may indeed function to increase genetic fidelity. However, the implications of asymmetric strand segregation for the fidelity of epigenetic information remain unexplored. Here, I explore the impact of strand-segregation dynamics on epigenetic fidelity using a mathematical-modelling approach that draws on the known molecular mechanisms of DNA methylation and existing rate estimates from empirical methylation data. I find that, for a wide range of starting methylation densities, asymmetric -- but not symmetric -- strand segregation leads to systematic increases in methylation levels if parent strands are subject to de novo methylation events. I found that epigenetic fidelity can be compromised when enhanced genetic fidelity is achieved through asymmetric strand segregation. Strand segregation dynamics could thus explain the increased DNA methylation densities that are observed in structured cellular populations during aging and in disease.

  11. Ideal 3D asymmetric concentrator

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Botella, Angel [Departamento Fisica Aplicada a los Recursos Naturales, Universidad Politecnica de Madrid, E.T.S.I. de Montes, Ciudad Universitaria s/n, 28040 Madrid (Spain); Fernandez-Balbuena, Antonio Alvarez; Vazquez, Daniel; Bernabeu, Eusebio [Departamento de Optica, Universidad Complutense de Madrid, Fac. CC. Fisicas, Ciudad Universitaria s/n, 28040 Madrid (Spain)

    2009-01-15

    Nonimaging optics is a field devoted to the design of optical components for applications such as solar concentration or illumination. In this field, many different techniques have been used for producing reflective and refractive optical devices, including reverse engineering techniques. In this paper we apply photometric field theory and elliptic ray bundles method to study 3D asymmetric - without rotational or translational symmetry - concentrators, which can be useful components for nontracking solar applications. We study the one-sheet hyperbolic concentrator and we demonstrate its behaviour as ideal 3D asymmetric concentrator. (author)

  12. Synthesis of New Chiral Benzimidazolylidene–Rh Complexes and Their Application in Asymmetric Addition Reactions of Organoboronic Acids to Aldehydes

    Directory of Open Access Journals (Sweden)

    Weiping He

    2016-09-01

    Full Text Available A series of novel chiral N-heterocyclic carbene rhodium complexes (NHC–Rh based on benzimidazole have been prepared, and all of the NHC–Rh complexes were fully characterized by NMR and mass spectrometry. These complexes could be used as catalysts for the asymmetric 1,2-addition of organoboronic acids to aldehydes, affording chiral diarylmethanols with high yields and moderate enantioselectivities.

  13. The asymmetric hetero-Diels-Alder reaction in the syntheses of biologically relevant compounds.

    Science.gov (United States)

    Eschenbrenner-Lux, Vincent; Kumar, Kamal; Waldmann, Herbert

    2014-10-13

    The hetero-Diels-Alder reaction is one of the most powerful transformations in the chemistry toolbox for the synthesis of aza- and oxa-heterocycles embodying multiple stereogenic centers. However, as compared to other cycloadditions, in particular the dipolar cycloadditions and the Diels-Alder reaction, the hetero-Diels-Alder reaction has been much less explored and exploited in organic synthesis. Nevertheless, this powerful transformation has opened up efficient and creative routes to biologically relevant small molecules and different natural products which contain six-membered oxygen or nitrogen ring systems. Recent developments in this field, in particular in the establishment of enantioselectively catalyzed hetero-Diels-Alder cycloadditions steered by a plethora of different catalysts and the application of the resulting small molecules in chemical biology and medicinal chemistry research, are highlighted in this Minireview. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Consistent and robust determination of border ownership based on asymmetric surrounding contrast.

    Science.gov (United States)

    Sakai, Ko; Nishimura, Haruka; Shimizu, Ryohei; Kondo, Keiichi

    2012-09-01

    Determination of the figure region in an image is a fundamental step toward surface construction, shape coding, and object representation. Localized, asymmetric surround modulation, reported neurophysiologically in early-to-intermediate-level visual areas, has been proposed as a mechanism for figure-ground segregation. We investigated, computationally, whether such surround modulation is capable of yielding consistent and robust determination of figure side for various stimuli. Our surround modulation model showed a surprisingly high consistency among pseudorandom block stimuli, with greater consistency for stimuli that yielded higher accuracy of, and shorter reaction times in, human perception. Our analyses revealed that the localized, asymmetric organization of surrounds is crucial in the detection of the contrast imbalance that leads to the determination of the direction of figure with respect to the border. The model also exhibited robustness for gray-scaled natural images, with a mean correct rate of 67%, which was similar to that of figure-side determination in human perception through a small window and of machine-vision algorithms based on local processing. These results suggest a crucial role of surround modulation in the local processing of figure-ground segregation. Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. Recyclable enantioselective catalysts based on copper(II) complexes of 2-(pyridine-2-yl)imidazolidine-4-thione: their application in asymmetric Henry reactions

    Czech Academy of Sciences Publication Activity Database

    Nováková, G.; Drabina, P.; Frumarová, Božena; Sedlák, M.

    2016-01-01

    Roč. 358, č. 15 (2016), s. 2541-2552 ISSN 1615-4150 Institutional support: RVO:61389013 Keywords : asymmetric catalysis * enantioselectivity * heterogeneous catalysis Subject RIV: CC - Organic Chemistry Impact factor: 5.646, year: 2016

  16. Asymmetric hindwing foldings in rove beetles.

    Science.gov (United States)

    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.

  17. Asymmetric Aldol Additions: A Guided-Inquiry Laboratory Activity on Catalysis

    Science.gov (United States)

    King, Jorge H. Torres; Wang, Hong; Yezierski, Ellen J.

    2018-01-01

    Despite the importance of asymmetric catalysis in both the pharmaceutical and commodity chemicals industries, asymmetric catalysis is under-represented in undergraduate chemistry laboratory curricula. A novel guided-inquiry experiment based on the asymmetric aldol addition was developed. Students conduct lab work to compare the effectiveness of…

  18. Parallel coupling of symmetric and asymmetric exclusion processes

    International Nuclear Information System (INIS)

    Tsekouras, K; Kolomeisky, A B

    2008-01-01

    A system consisting of two parallel coupled channels where particles in one of them follow the rules of totally asymmetric exclusion processes (TASEP) and in another one move as in symmetric simple exclusion processes (SSEP) is investigated theoretically. Particles interact with each other via hard-core exclusion potential, and in the asymmetric channel they can only hop in one direction, while on the symmetric lattice particles jump in both directions with equal probabilities. Inter-channel transitions are also allowed at every site of both lattices. Stationary state properties of the system are solved exactly in the limit of strong couplings between the channels. It is shown that strong symmetric couplings between totally asymmetric and symmetric channels lead to an effective partially asymmetric simple exclusion process (PASEP) and properties of both channels become almost identical. However, strong asymmetric couplings between symmetric and asymmetric channels yield an effective TASEP with nonzero particle flux in the asymmetric channel and zero flux on the symmetric lattice. For intermediate strength of couplings between the lattices a vertical-cluster mean-field method is developed. This approximate approach treats exactly particle dynamics during the vertical transitions between the channels and it neglects the correlations along the channels. Our calculations show that in all cases there are three stationary phases defined by particle dynamics at entrances, at exits or in the bulk of the system, while phase boundaries depend on the strength and symmetry of couplings between the channels. Extensive Monte Carlo computer simulations strongly support our theoretical predictions. Theoretical calculations and computer simulations predict that inter-channel couplings have a strong effect on stationary properties. It is also argued that our results might be relevant for understanding multi-particle dynamics of motor proteins

  19. Multipartite asymmetric quantum cloning

    International Nuclear Information System (INIS)

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

    2005-01-01

    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 A clones with fidelity F A and another set of M B clones with fidelity F B , the trade-off between these fidelities is analyzed, and particular cases of optimal N→M A +M B cloning machines are exhibited. We also present an optimal 1→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

  20. Seasonally asymmetric enhancement of northern vegetation productivity

    Science.gov (United States)

    Park, T.; Myneni, R.

    2017-12-01

    Multiple evidences of widespread greening and increasing terrestrial carbon uptake have been documented. In particular, enhanced gross productivity of northern vegetation has been a critical role leading to observed carbon uptake trend. However, seasonal photosynthetic activity and its contribution to observed annual carbon uptake trend and interannual variability are not well understood. Here, we introduce a multiple-source of datasets including ground, atmospheric and satellite observations, and multiple process-based global vegetation models to understand how seasonal variation of land surface vegetation controls a large-scale carbon exchange. Our analysis clearly shows a seasonally asymmetric enhancement of northern vegetation productivity in growing season during last decades. Particularly, increasing gross productivity in late spring and early summer is obvious and dominant driver explaining observed trend and variability. We observe more asymmetric productivity enhancement in warmer region and this spatially varying asymmetricity in northern vegetation are likely explained by canopy development rate, thermal and light availability. These results imply that continued warming may facilitate amplifying asymmetric vegetation activity and cause these trends to become more pervasive, in turn warming induced regime shift in northern land.

  1. Asymmetric Price Responses of Gasoline Stations. Evidence for Heterogeneity of Retailers

    Energy Technology Data Exchange (ETDEWEB)

    Faber, R.P. [Erasmus University Rotterdam, Rotterdam (Netherlands)

    2009-11-15

    This paper studies asymmetric price responses of individual firms, via daily retail prices of almost all gasoline stations in the Netherlands and suggested prices of the five largest oil companies over more than two years. I find that 38% of the stations respond asymmetrically to changes in the spot market price. Hence, asymmetric pricing is not a feature of the market as a whole, but of individual firms. For asymmetrically pricing stations, the asymmetry is substantial directly after a change but disappears after one or two days. I study station-specific characteristics and conclude that asymmetric pricing seems to be a phenomenon that is randomly distributed across stations. I also find that none of the five largest oil companies adjust their suggested prices asymmetrically.

  2. Asymmetric Price Responses of Gasoline Stations. Evidence for Heterogeneity of Retailers

    International Nuclear Information System (INIS)

    Faber, R.P.

    2009-11-01

    This paper studies asymmetric price responses of individual firms, via daily retail prices of almost all gasoline stations in the Netherlands and suggested prices of the five largest oil companies over more than two years. I find that 38% of the stations respond asymmetrically to changes in the spot market price. Hence, asymmetric pricing is not a feature of the market as a whole, but of individual firms. For asymmetrically pricing stations, the asymmetry is substantial directly after a change but disappears after one or two days. I study station-specific characteristics and conclude that asymmetric pricing seems to be a phenomenon that is randomly distributed across stations. I also find that none of the five largest oil companies adjust their suggested prices asymmetrically.

  3. Observation of asymmetric electromagnetic field profiles in chiral metamaterials

    Science.gov (United States)

    Hisamoto, Nobuyuki; Ueda, Tetsuya; Sawada, Kei; Tomita, Satoshi

    2018-02-01

    We experimentally observe asymmetric electromagnetic field profiles along two-dimensional chiral metamaterials. The asymmetric field profiles depending on the chirality and the operation frequency have been reproduced well by the numerical simulation. Around a chiral meta-atom, distribution of a Poynting vector is found to be shifted asymmetrically. These results are explained in terms of an analogy with the side-jump mechanism in the electronic anomalous Hall systems.

  4. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei

    2016-10-13

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.

  5. Reversal of the sense of enantioselectivity between 1-and 2-aza[6]helicenes used as chiral inducers of asymmetric autocatalysis

    Czech Academy of Sciences Publication Activity Database

    Matsumoto, A.; Yonemitsu, K.; Ozaki, H.; Míšek, Jiří; Starý, Ivo; Stará, Irena G.; Soai, K.

    2017-01-01

    Roč. 15, č. 6 (2017), s. 1321-1324 ISSN 1477-0520 R&D Projects: GA ČR(CZ) GA14-29667S Institutional support: RVO:61388963 Keywords : azahelicene * Soai reaction * asymmetric autocatalysis Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 3.564, year: 2016 http://pubs.rsc.org/en/content/articlehtml/2013/ob/c6ob02745h

  6. Analytical relations between nuclear symmetry energy and single-nucleon potentials in isospin asymmetric nuclear matter

    International Nuclear Information System (INIS)

    Xu Chang; Li Baoan; Chen Liewen; Ko, Che Ming

    2011-01-01

    Using the Hugenholtz-Van Hove theorem, we derive general expressions for the quadratic and quartic symmetry energies in terms of the isoscalar and isovector parts of single-nucleon potentials in isospin asymmetric nuclear matter. These expressions are useful for gaining deeper insights into the microscopic origins of the uncertainties in our knowledge on nuclear symmetry energies especially at supra-saturation densities. As examples, the formalism is applied to two model single-nucleon potentials that are widely used in transport model simulations of heavy-ion reactions.

  7. A new convenient asymmetric approach to herbarumin Ⅲ

    Institute of Scientific and Technical Information of China (English)

    Xue Song Chen; Shi Jun Da; Li Hong Yang; Bo Yan Xu; Zhi Xiang Xie; Ying Li

    2007-01-01

    The asymmetric total synthesis of herbarumin Ⅲ 3, a naturally occurred phytotoxin, along with 8-epi-herbarumin Ⅲ 22, was succeeded in 12 steps from n-butyraldehyde based on Brown's asymmetric allylation, taking modified Julia olefination and Yamaguchi's macro-lactonization as key steps.

  8. Fourier synthesis of asymmetrical optical potentials for atoms

    International Nuclear Information System (INIS)

    Ritt, G.

    2007-01-01

    In this work a dissipationless asymmetrical optical potential for cold atoms was produced. In a first step a new type of optical lattice was generated, whose spatial periodicity only corresponds to a quarter of the wavelength of the light used for the generation. This corresponds to the half of the periodicity of a conventional optical lattice, which is formed by the light of the same wavelength. The generation of this new type of optical lattice was reached by the use of two degenerated raman transitions. Virtual processes occur, in which four photons are involved. In conventional optical lattices however virtual two-photon processes occur. By spatially superimposing this optical lattice with a conventional optical lattice an asymmetrical optical potential could be formed. By diffraction of a Bose Einstein condensate of rubidium atoms at the transient activated asymmetrical potential the asymmetrical structure was proven. (orig.)

  9. Engineered Asymmetric Composite Membranes with Rectifying Properties.

    Science.gov (United States)

    Wen, Liping; Xiao, Kai; Sainath, Annadanam V Sesha; Komura, Motonori; Kong, Xiang-Yu; Xie, Ganhua; Zhang, Zhen; Tian, Ye; Iyoda, Tomokazu; Jiang, Lei

    2016-01-27

    Asymmetric composite membranes with rectifying properties are developed by grafting pH-stimulus-responsive materials onto the top layer of the composite structure, which is prepared by two novel block copolymers using a phase-separation technique. This engineered asymmetric composite membrane shows potential applications in sensors, filtration, and nanofluidic devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Variable angle asymmetric cut monochromator

    International Nuclear Information System (INIS)

    Smither, R.K.; Fernandez, P.B.

    1993-09-01

    A variable incident angle, asymmetric cut, double crystal monochromator was tested for use on beamlines at the Advanced Photon Source (APS). For both undulator and wiggler beams the monochromator can expand area of footprint of beam on surface of the crystals to 50 times the area of incident beam; this will reduce the slope errors by a factor of 2500. The asymmetric cut allows one to increase the acceptance angle for incident radiation and obtain a better match to the opening angle of the incident beam. This can increase intensity of the diffracted beam by a factor of 2 to 5 and can make the beam more monochromatic, as well. The monochromator consists of two matched, asymmetric cut (18 degrees), silicon crystals mounted so that they can be rotated about three independent axes. Rotation around the first axis controls the Bragg angle. The second rotation axis is perpendicular to the diffraction planes and controls the increase of the area of the footprint of the beam on the crystal surface. Rotation around the third axis controls the angle between the surface of the crystal and the wider, horizontal axis for the beam and can make the footprint a rectangle with a minimum. length for this area. The asymmetric cut is 18 degrees for the matched pair of crystals, which allows one to expand the footprint area by a factor of 50 for Bragg angles up to 19.15 degrees (6 keV for Si[111] planes). This monochromator, with proper cooling, will be useful for analyzing the high intensity x-ray beams produced by both undulators and wigglers at the APS

  11. Asymmetric synthesis with microbes; Biseibutsu wo katsuyoshita kogaku kassei kagobutsu no koritsutekina gosei

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, S. [Ritsumeikan Univ., Tokyo (Japan). Faculty of Science and Engineering

    1996-02-01

    Use of microbial enzymes have been widely extended as an effective means for asymmetric synthesis. However, the asymmetric selectivity often decreases due to competitive catalysis among plural enzymes in a microbe. The author has been studied development of methods for control of the stereo-selectivity using subtle difference of enzyme characteristics. When Michaelis constant (Km) differs between two enzymes, one enzyme of lower Km becomes active with decrease in concentration of substrate, expressing its stereo-selectivity. Reduction of {alpha}-ketoesters in water by bread yeast (Saccharomyces cerevisiae) yields products of S-configuration, whereas those of R-configuration are obtained in an organic solvent in the presence of small amount of water. This is because reaction field of the yeast is in water and because R-configuration enzyme of lower Km works for substrate whose concentration in water has decreased due to two phase partition of organic solvent and water system. Further, use of difference of decrease in enzyme activity by inhibitors in stereo-selective synthesis of {alpha}-hydroxyketones (I) from {alpha}-diketone and use of difference of thermal endurance in improvement of formation ratio among I, are also introduced. 6 refs., 3 figs., 2 tabs.

  12. Decrease in back strength in asymmetric trunk postures

    NARCIS (Netherlands)

    Vink, P.; Daanen, H. A M; Meijst, W. J.; Ligteringen, J.

    1992-01-01

    The extension force against resistance was recorded in 23 postures for 12 subjects to find explanations for the decrease in back strength in asymmetric postures. A reduction in muscle force in asymmetric postures was found up to 40%, but was strongly dependent on the plane in which asymmetry

  13. Enantioselective organocatalyzed Oxa-Michael-Aldol cascade reactions: Construction of chiral 4H-chromenes with a trifluoromethylated tetrasubstituted carbon stereocenter

    KAUST Repository

    Zhang, Jing; Ajitha, Manjaly John; He, Lin; Liu, Kai; Dai, Bin; Huang, Kuo-Wei

    2015-01-01

    The first organocatalytic asymmetric synthesis of 4H-chromenes bearing a trifluoromethylated tetrasubstituted carbon center is presented. Chiral secondary amines promote the oxa-Michael-aldol cascade reaction between alkynals and 2

  14. Asymmetric Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene

    Directory of Open Access Journals (Sweden)

    Magnus Rueping

    2012-10-01

    Full Text Available A new chiral Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene has been developed. The reaction provides optically active aza-tetracycles in good yields with high diastereo- and enantioselectivities under mild reaction conditions.

  15. The application of green chemistry methods in organophosphorus synthesis

    International Nuclear Information System (INIS)

    Odinets, Irina L; Matveeva, E V

    2012-01-01

    Data concerning the synthesis of organophosphorus compounds in ionic liquids, in water and under solvent-free conditions are considered and summarized. It is shown that this strategy, which complies with the definition of green chemistry, has advantages in terms of the rate of the process and the yields of target products as compared with syntheses in common organic solvents. The Wittig, Horner–Wadsworth–Emmons, Kabachnik–Fields, Arbuzov and Michaelis reactions are considered as examples. The bibliography includes 178 references.

  16. Subglottic cysts and asymmetrical subglottic narrowing on neck radiograph

    International Nuclear Information System (INIS)

    Holinger, L.D.; Torium, D.M.; Anandappa, E.C.

    1988-01-01

    The congenital subglottic hemangioma typically appears as an asymmetric subglottic narrowing or mass on frontal neck radiograph. Therefore, soft tissue neck radiography has been advocated as a definitive non-operative approach for diagnosing these lesions. However, we have noted similar asymmetric subglottic narrowing in patients with acquired subglottic cysts. These retention cysts occur following long-term intubation in the neonate. The mechanism probably involves subglottic fibrosis which obstructs glands with subsequent cyst formation. Acquired subglottic cysts typically appear as an asymmetric narrowing on frontal or lateral soft tissue neck radiographs. These lesions may produce airway compromise but are effectively treated by forceps or laser removal. Acquired subglottic cysts must be included in the differential diagnosis of asymmetric subglottic narrowing. The definitive diagnosis is made by direct laryngoscopy, not soft tissue neck radiograph. (orig.)

  17. Application of the aza-Diels-Alder reaction in the synthesis of natural products.

    Science.gov (United States)

    Cao, Min-Hui; Green, Nicholas J; Xu, Sheng-Zhen

    2017-04-11

    The Diels-Alder reaction that involves a nitrogen atom in the diene or dienophile is termed the aza-Diels-Alder reaction. As well as the powerful all-carbon Diels-Alder reaction, the aza-Diels-Alder reaction has also played an important role in the total synthesis of natural products. Herein, we review various natural products using an aza-Diels-Alder reaction as a key step to their total synthesis, and divide the syntheses into inter- and intra-molecular aza-Diels-Alder reactions and a retro-aza-Diels-Alder reaction. Inter- and intra-molecular aza-Diels-Alder reactions involve an imine as an electron deficient dienophile and an imine as an electron deficient azadiene. The significance of the aza-Diels-Alder reaction for the construction of a six-membered ring containing nitrogen is tremendous, but the development of asymmetric, in particular catalytic enantioselective intramolecular aza-Diels-Alder reaction in the total synthesis of natural products remains highly challenging, and will no doubt see enormous advances in the future.

  18. Lower Bounds in the Asymmetric External Memory Model

    DEFF Research Database (Denmark)

    Jacob, Riko; Sitchinava, Nodari

    2017-01-01

    Motivated by the asymmetric read and write costs of emerging non-volatile memory technologies, we study lower bounds for the problems of sorting, permuting and multiplying a sparse matrix by a dense vector in the asymmetric external memory model (AEM). Given an AEM with internal (symmetric) memory...... of size M, transfers between symmetric and asymmetric memory in blocks of size B and the ratio ω between write and read costs, we show Ω(min (N, ωN/B logω M/B N/B) lower bound for the cost of permuting N input elements. This lower bound also applies to the problem of sorting N elements. This proves...

  19. Ultrathin-skinned asymmetric membranes by immiscible solvents treatment

    Science.gov (United States)

    Friesen, Dwayne T.; Babcock, Walter C.

    1989-01-01

    Improved semipermeable asymmetric fluid separation membranes useful in gas, vapor and liquid separations are disclosed. The membranes are prepared by substantially filling the pores of asymmetric cellulosic semipermeable membranes having a finely porous layer on one side thereof with a water immiscible organic liquid, followed by contacting the finely porous layer with water.

  20. Asymmetric conditional volatility in international stock markets

    Science.gov (United States)

    Ferreira, Nuno B.; Menezes, Rui; Mendes, Diana A.

    2007-08-01

    Recent studies show that a negative shock in stock prices will generate more volatility than a positive shock of similar magnitude. The aim of this paper is to appraise the hypothesis under which the conditional mean and the conditional variance of stock returns are asymmetric functions of past information. We compare the results for the Portuguese Stock Market Index PSI 20 with six other Stock Market Indices, namely the SP 500, FTSE 100, DAX 30, CAC 40, ASE 20, and IBEX 35. In order to assess asymmetric volatility we use autoregressive conditional heteroskedasticity specifications known as TARCH and EGARCH. We also test for asymmetry after controlling for the effect of macroeconomic factors on stock market returns using TAR and M-TAR specifications within a VAR framework. Our results show that the conditional variance is an asymmetric function of past innovations raising proportionately more during market declines, a phenomenon known as the leverage effect. However, when we control for the effect of changes in macroeconomic variables, we find no significant evidence of asymmetric behaviour of the stock market returns. There are some signs that the Portuguese Stock Market tends to show somewhat less market efficiency than other markets since the effect of the shocks appear to take a longer time to dissipate.

  1. Salt supply to and significance of asymmetric salt diapirs

    DEFF Research Database (Denmark)

    Koyi, H.; Burliga, S.; Chemia, Zurab

    2012-01-01

    Salt diapirs can be asymmetric both internally and externally reflecting their evolution history. As such, this asymmetry bear a significant amount of information about the differential loading (± lateral forces) and in turn the salt supply that have shaped the diapir. In two dimensions......, In this study we compare results of analogue and numerical models of diapirs with two natural salt diapris (Klodawa and Gorleben diapirs) to explain their salt supply and asymmetric evolution. In a NW-SE section, the Gorleben salt diapir possesses an asymmetric external geometry represented by a large...... southeastern overhang due to salt extrusion during Middle Cretaceous followed by its burial in Tertiary. This external asymmetry is also reflected in the internal configuration of the diapir which shows different rates of salt flow on the two halves of the structure. The asymmetric external and internal...

  2. Two-channel totally asymmetric simple exclusion processes

    International Nuclear Information System (INIS)

    Pronina, Ekaterina; Kolomeisky, Anatoly B

    2004-01-01

    Totally asymmetric simple exclusion processes, consisting of two coupled parallel lattice chains with particles interacting with hard-core exclusion and moving along the channels and between them, are considered. In the limit of strong coupling between the channels, the particle currents, density profiles and a phase diagram are calculated exactly by mapping the system into an effective one-channel totally asymmetric exclusion model. For intermediate couplings, a simple approximate theory, that describes the particle dynamics in vertical clusters of two corresponding parallel sites exactly and neglects the correlations between different vertical clusters, is developed. It is found that, similarly to the case of one-channel totally asymmetric simple exclusion processes, there are three stationary state phases, although the phase boundaries and stationary properties strongly depend on inter-channel coupling. Extensive computer Monte Carlo simulations fully support the theoretical predictions

  3. Appropriate quantization of asymmetric games with continuous strategies

    International Nuclear Information System (INIS)

    Qin Gan; Chen Xi; Sun Min; Zhou Xianyi; Du Jiangfeng

    2005-01-01

    We establish a new quantization scheme to study the asymmetric Bertrand duopoly with differentiated products. This scheme is more efficient than the previous symmetric one because it can exactly make the optimal cooperative payoffs at quantum Nash equilibrium. It is also a necessary condition for general asymmetric games with continuous strategies to reach such payoffs

  4. Asymmetric forecasting and commitment policy in a robust control problem

    OpenAIRE

    Taro Ikeda

    2013-01-01

    This paper provides a piece of results regarding asymmetric forecasting and commitment monetary policy with a robust control algorithm. Previous studies provide no clarification of the connection between asymmetric preference and robust commitment policy. Three results emerge from general equilibrium modeling with asymmetric preference: (i) the condition for system stability implies an average inflation bias with respect to asymmetry (ii) the effect of asymmetry can be mitigated if policy mak...

  5. Immobilization of Acetobacter sp. CCTCC M209061 for efficient asymmetric reduction of ketones and biocatalyst recycling.

    Science.gov (United States)

    Chen, Xiao-Hong; Wang, Xiao-Ting; Lou, Wen-Yong; Li, Ying; Wu, Hong; Zong, Min-Hua; Smith, Thomas J; Chen, Xin-De

    2012-09-04

    The bacterium Acetobacter sp. CCTCC M209061 is a promising whole-cell biocatalyst with exclusive anti-Prelog stereoselectivity for the reduction of prochiral ketones that can be used to make valuable chiral alcohols such as (R)-4-(trimethylsilyl)-3-butyn-2-ol. Although it has promising catalytic properties, its stability and reusability are relatively poor compared to other biocatalysts. Hence, we explored various materials for immobilizing the active cells, in order to improve the operational stability of biocatalyst. It was found that Ca-alginate give the best immobilized biocatalyst, which was then coated with chitosan to further improve its mechanical strength and swelling-resistance properties. Conditions were optimized for formation of reusable immobilized beads which can be used for repeated batch asymmetric reduction of 4'-chloroacetophenone. The optimized immobilized biocatalyst was very promising, with a specific activity of 85% that of the free-cell biocatalyst (34.66 μmol/min/g dw of cells for immobilized catalyst vs 40.54 μmol/min/g for free cells in the asymmetric reduction of 4'-chloroacetophenone). The immobilized cells showed better thermal stability, pH stability, solvent tolerance and storability compared with free cells. After 25 cycles reaction, the immobilized beads still retained >50% catalytic activity, which was 3.5 times higher than degree of retention of activity by free cells reused in a similar way. The cells could be recultured in the beads to regain full activity and perform a further 25 cycles of the reduction reaction. The external mass transfer resistances were negligible as deduced from Damkohler modulus Da internal mass transfer restriction affected the reduction action but was not the principal rate-controlling step according to effectiveness factors η < 1 and Thiele modulus 0.3<∅ <1. Ca-alginate coated with chitosan is a highly effective material for immobilization of Acetobacter sp. CCTCC M209061 cells for repeated use in

  6. Immobilization of Acetobacter sp. CCTCC M209061 for efficient asymmetric reduction of ketones and biocatalyst recycling

    Directory of Open Access Journals (Sweden)

    Chen Xiao-Hong

    2012-09-01

    Full Text Available Abstract Background The bacterium Acetobacter sp. CCTCC M209061 is a promising whole-cell biocatalyst with exclusive anti-Prelog stereoselectivity for the reduction of prochiral ketones that can be used to make valuable chiral alcohols such as (R-4-(trimethylsilyl-3-butyn-2-ol. Although it has promising catalytic properties, its stability and reusability are relatively poor compared to other biocatalysts. Hence, we explored various materials for immobilizing the active cells, in order to improve the operational stability of biocatalyst. Results It was found that Ca-alginate give the best immobilized biocatalyst, which was then coated with chitosan to further improve its mechanical strength and swelling-resistance properties. Conditions were optimized for formation of reusable immobilized beads which can be used for repeated batch asymmetric reduction of 4′-chloroacetophenone. The optimized immobilized biocatalyst was very promising, with a specific activity of 85% that of the free-cell biocatalyst (34.66 μmol/min/g dw of cells for immobilized catalyst vs 40.54 μmol/min/g for free cells in the asymmetric reduction of 4′-chloroacetophenone. The immobilized cells showed better thermal stability, pH stability, solvent tolerance and storability compared with free cells. After 25 cycles reaction, the immobilized beads still retained >50% catalytic activity, which was 3.5 times higher than degree of retention of activity by free cells reused in a similar way. The cells could be recultured in the beads to regain full activity and perform a further 25 cycles of the reduction reaction. The external mass transfer resistances were negligible as deduced from Damkohler modulus Da η ∅ Conclusions Ca-alginate coated with chitosan is a highly effective material for immobilization of Acetobacter sp. CCTCC M209061 cells for repeated use in the asymmetric reduction of ketones. Only a small cost in terms of the slightly lower catalytic activity compared to

  7. How Is Nature Asymmetric?

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 7; Issue 6. How Is Nature Asymmetric? - Discrete Symmetries in Particle Physics and their Violation ... Indian Institute of Technology, Chennai. Aligarh Muslim University. University of Rajasthan, Jaipur. Indian Institute of Science, Bangalore 560012, India.

  8. Exploring asymmetric catalytic transformations

    NARCIS (Netherlands)

    Guduguntla, Sureshbabu

    2017-01-01

    In Chapter 2, we report a highly enantioselective synthesis of β-alkyl-substituted alcohols through a one-pot Cu- catalyzed asymmetric allylic alkylation with organolithium reagents followed by reductive ozonolysis. The synthesis of γ-alkyl-substituted alcohols was also achieved through Cu-catalyzed

  9. Simulation of Phenix EOL Asymmetric Test

    Energy Technology Data Exchange (ETDEWEB)

    Ha, Kwi Seok; Lee, Kwi Lim; Choi, Chi Woong; Kang, Seok Hun; Chang, Won Pyo; Jeong, Hae Yong [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2012-05-15

    The asymmetric test of End-Of-Life (EOL) tests on the Phenix plant was used for the evaluation of the MARS-LMR in the Generation IV frame as a part of the code validation. The purpose of the test is to evaluate the ability of the system code to describe asymmetric situations and to identify important phenomena during asymmetrical transient such as a three dimensional effect, buoyancy influence, and thermal stratification in the hot and cold pools. 3-dimensional sodium coolant mixing in the pools has different characteristics from the one dimensional full instantaneous mixing. The velocities and temperatures at the core outlet level differ at each sub-assembly and the temperature in the center of the hot pool may be high because the driver fuels are located at the center region. The temperatures in the hot pool are not the same in the radial and axial locations due to the buoyancy effect. The temperatures in the cold pool also differ along with the elevations and azimuthal directions due to the outlet location of IHX and the thermal stratification

  10. Flatfish: an asymmetric perspective on metamorphosis.

    Science.gov (United States)

    Schreiber, Alexander M

    2013-01-01

    The most asymmetrically shaped and behaviorally lateralized of all the vertebrates, the flatfishes are an endless source of fascination to all fortunate enough to study them. Although all vertebrates undergo left-right asymmetric internal organ placement during embryogenesis, flatfish are unusual in that they experience an additional period of postembryonic asymmetric remodeling during metamorphosis, and thus deviate from a bilaterally symmetrical body plan more than other vertebrates. As with amphibian metamorphosis, all the developmental programs of flatfish metamorphosis are ultimately under the control of thyroid hormone. At least one gene pathway involved in embryonic organ lateralization (nodal-lefty-pitx2) is re-expressed in the larval stage during flatfish metamorphosis. Aspects of modern flatfish ontogeny, such as the gradual translocation of one eye to the opposite side of the head and the appearance of key neurocranial elements during metamorphosis, seem to elegantly recapitulate flatfish phylogeny. This chapter highlights the current state of knowledge of the developmental biology of flatfish metamorphosis with emphases on the genetic, morphological, behavioral, and evolutionary origins of flatfish asymmetry. Copyright © 2013 Elsevier Inc. All rights reserved.

  11. Standards vs. labels with imperfect competition and asymmetric information

    DEFF Research Database (Denmark)

    Baltzer, Kenneth Thomas

    2012-01-01

    I demonstrate that providing information about product quality is not necessarily the best way to address asymmetric information problems when markets are imperfectly competitive. In a vertical differentiation model I show that a Minimum Quality Standard, which retains asymmetric information...

  12. Standards vs. labels with imperfect competition and asymmetric information

    DEFF Research Database (Denmark)

    Baltzer, Kenneth Thomas

    I demonstrate that providing information about product quality is not necessarily the best way to address asymmetric information problems when markets are imperfectly competitive. In a vertical dierentiation model I show that a Minimum Quality Standard, which retains asymmetric information...

  13. Comparison of 3D Classical Trajectory and Transition-State Theory Reaction Cross Sections

    Science.gov (United States)

    Koeppl, G. W.; Karplus, Martin

    1970-10-01

    Although there is excellent agreement for a system such as H+H{sub 2} --> H{sub 2}+H, in which both the potential and the particle masses are symmetric, significant deviations occur for more asymmetric reactions. A detailed analysis show that the calculated differences are from the violation of two assumptions of transition-state theory.

  14. Asymmetrical Polymer Vesicles for Drug delivery and Other Applications

    Directory of Open Access Journals (Sweden)

    Yi Zhao

    2017-06-01

    Full Text Available Scientists have been attracted by polymersomes as versatile drug delivery systems since the last two decades. Polymersomes have the potential to be versatile drug delivery systems because of their tunable membrane formulations, stabilities in vivo, various physicochemical properties, controlled release mechanisms, targeting abilities, and capacities to encapsulate a wide range of drugs and other molecules. Asymmetrical polymersomes are nano- to micro-sized polymeric capsules with asymmetrical membranes, which means, they have different outer and inner coronas so that they can exhibit better endocytosis rate and endosomal escape ability than other polymeric systems with symmetrical membranes. Hence, asymmetrical polymersomes are highly promising as self-assembled nano-delivery systems in the future for in vivo therapeutics delivery and diagnostic imaging applications. In this review, we prepared a summary about recent research progresses of asymmetrical polymersomes in the following aspects: synthesis, preparation, applications in drug delivery and others.

  15. Dynamical Dipole and Equation of State in N/Z Asymmetric Fusion Reactions

    Directory of Open Access Journals (Sweden)

    Giaz Agnese

    2014-03-01

    Full Text Available In heavy ion reactions, in the case of N/Z asymmetry between projectile and target, the process leading to complete fusion is expected to produce pre-equilibrium dipole γ-ray emission. It is generated during the charge equilibration process and it is known as Dynamical Dipole. A new measurement of the dynamical dipole emission was performed by studying 16O + 116Sn at 12 MeV/u. These data, together with those measured at 8.1 MeV/u and 15.6 MeV/u for the same reaction, provide the dependence on the Dynamical Dipole total emission yield with beam energy and they can be compared with theoretical expectations. The experimental results show a weak increase of the Dynamical Dipole total yield with beam energies and are in agreement with the prediction of a theoretical model based on the Boltzmann–Nordheim–Vlasov (BNV approach. The measured trend with beam energy does not confirm the rise and fall behavior previously reported for the same fused compound but with a much higher dipole moment.

  16. Fabrication of Bi2O3||AC asymmetric supercapacitor with redox additive aqueous electrolyte and its improved electrochemical performances

    International Nuclear Information System (INIS)

    Senthilkumar, S.T.; Selvan, R. Kalai; Ulaganathan, M.; Melo, J.S.

    2014-01-01

    Graphical abstract: An asymmetric supercapacitor (ASC) has been fabricated using α-Bi 2 O 3 and bio-waste derived activated carbon (AC) as negative and positive electrodes respectively with Li 2 SO 4 as electrolyte. Interestingly, the addition of KI into the Li 2 SO 4 electrolyte can significantly enhances the ASC performance through the redox reaction between iodine/iodide ions. -- Highlights: •Flower like α-Bi 2 O 3 is prepared. •An asymmetric supercapacitor is fabricated using α-Bi 2 O 3 as negative electrode and bio-waste derived activated carbon as positive electrode. •Energy density is enhanced from 10.2 Wh kg −1 to 35.4 Wh kg −1 by using KI as redox additive in Li 2 SO 4 electrolyte. -- Abstract: A new asymmetric supercapacitor (ASC) was fabricated using flower like α-Bi2O3as negative and bio-waste derived activated carbon (AC) as positive electrodes with Li2SO4as electrolyte. Here, the fabricated ASC was operated over the potential range of 0-1.6 V and evaluated by cyclic voltammetry (CV), galvano static charge-discharge (GCD), electrochemical impedance spectroscopy (EIS) and cycle life. Further to improve the performance of ASC, KI was used as electrolyte redox additive with pristine (Li2SO4) electrolyte due to their possible redox reactions of iodine ions. Remarkably, a nearly threefold improved specific capacitance and energy density of 99.5 F g −1 and 35.4 Wh kg −1 respectively was achieved by adding of KI into Li 2 SO 4 electrolyte, while it was only 29 F g −1 and 10.2 Wh kg −1 for pristine (Li2SO4) electrolyte used ASC at 1.5 mA cm −2

  17. Origin of Exo/Endo Selectivity in the Intramolecular Diels-Alder Reaction

    International Nuclear Information System (INIS)

    Yan, Shihai; Ryu, Do Hyun; Lee, Jin Yong

    2010-01-01

    The stereoselectivity of the intramolecular Diels-Alder reactions of 1 and its derivatives were investigated by ab initio calculations. The stereoselectivity mainly originates from the steric repulsion and the orbital interactions. The additional s-cis and s-trans conformations by introducing the carbonyl group at the neighbor of diene or dienophile may change the stereoselectivity, hence this kind of substitution can be utilized for stereoselective asymmetric synthesis

  18. Cell Chirality Drives Left-Right Asymmetric Morphogenesis.

    Science.gov (United States)

    Inaki, Mikiko; Sasamura, Takeshi; Matsuno, Kenji

    2018-01-01

    Most macromolecules found in cells are chiral, meaning that they cannot be superimposed onto their mirror image. However, cells themselves can also be chiral, a subject that has received little attention until very recently. In our studies on the mechanisms of left-right (LR) asymmetric development in Drosophila , we discovered that cells can have an intrinsic chirality to their structure, and that this "cell chirality" is generally responsible for the LR asymmetric development of certain organs in this species. The actin cytoskeleton plays important roles in the formation of cell chirality. In addition, Myosin31DF ( Myo31DF ), which encodes Drosophila Myosin ID, was identified as a molecular switch for cell chirality. In other invertebrate species, including snails and Caenorhabditis elegans , chirality of the blastomeres, another type of cell chirality, determines the LR asymmetry of structures in the body. Thus, chirality at the cellular level may broadly contribute to LR asymmetric development in various invertebrate species. Recently, cell chirality was also reported for various vertebrate cultured cells, and studies suggested that cell chirality is evolutionarily conserved, including the essential role of the actin cytoskeleton. Although the biological roles of cell chirality in vertebrates remain unknown, it may control LR asymmetric development or other morphogenetic events. The investigation of cell chirality has just begun, and this new field should provide valuable new insights in biology and medicine.

  19. Use of nonlinear asymmetrical shock absorber to improve comfort on passenger vehicles

    Science.gov (United States)

    Silveira, M.; Pontes, B. R.; Balthazar, J. M.

    2014-03-01

    In this study the behaviour of two different types of shock absorbers, symmetrical (linear) and asymmetrical (nonlinear) is compared for use on passenger vehicles. The analyses use different standard road inputs and include variation of the severity parameter, the asymmetry ratio and the velocity of the vehicle. Performance indices and acceleration values are used to assess the efficacy of the asymmetrical systems. The comparisons show that the asymmetrical system, with nonlinear characteristics, tends to have a smoother and more progressive performance, both for vertical and angular movements. The half-car front asymmetrical system was introduced, and the simulation results show that the use of the asymmetrical system only at the front of the vehicle can further diminish the angular oscillations. As lower levels of acceleration are essential for improved ride comfort, the use of asymmetrical systems for vibrations and impact absorption can be a more advantageous choice for passenger vehicles.

  20. Performance of JPEG Image Transmission Using Proposed Asymmetric Turbo Code

    Directory of Open Access Journals (Sweden)

    Siddiqi Mohammad Umar

    2007-01-01

    Full Text Available This paper gives the results of a simulation study on the performance of JPEG image transmission over AWGN and Rayleigh fading channels using typical and proposed asymmetric turbo codes for error control coding. The baseline JPEG algorithm is used to compress a QCIF ( "Suzie" image. The recursive systematic convolutional (RSC encoder with generator polynomials , that is, (13/11 in decimal, and 3G interleaver are used for the typical WCDMA and CDMA2000 turbo codes. The proposed asymmetric turbo code uses generator polynomials , that is, (13/11; 13/9 in decimal, and a code-matched interleaver. The effect of interleaver in the proposed asymmetric turbo code is studied using weight distribution and simulation. The simulation results and performance bound for proposed asymmetric turbo code for the frame length , code rate with Log-MAP decoder over AWGN channel are compared with the typical system. From the simulation results, it is observed that the image transmission using proposed asymmetric turbo code performs better than that with the typical system.

  1. Asymmetric Modeling of the Industrial Heavy Water Plant (PIAP)

    International Nuclear Information System (INIS)

    Teruel, Federico; Aprea, J; Guido Lavalle, German

    2000-01-01

    Software of asymmetric stationary simulation for the Industrial Heavy Water Plant (PIAP) was developed, based on an existing symmetric simulator (Brigitte 2.0).This software allows to turn off some of the isotopic enrichment twin units present in the plant and to simulate them asymmetrically, in other words, with different selection of parameters between twins.Other incorporations were done, such as passing flows between units and entering flows in strategic points of the plant.The iterative system in which the symmetric simulator is based was insufficient to develop the asymmetric simulator, so the system was modeled according to an implicit scheme for the units that form the simulator.This type of resolution resulted in a simulator that supports a big range of boundary conditions and internal parameters.Moreover, the time of calculus is short (∼3 minutes), making it actually useful.The asymmetric simulator is at the PIAP now, for its study and validation. It shows expected tendencies and results according to the symmetric simulator already validated

  2. Simple synthesis of amorphous NiWO4 nanostructure and its application as a novel cathode material for asymmetric supercapacitors.

    Science.gov (United States)

    Niu, Lengyuan; Li, Zhangpeng; Xu, Ye; Sun, Jinfeng; Hong, Wei; Liu, Xiaohong; Wang, Jinqing; Yang, Shengrong

    2013-08-28

    This study reports a simple synthesis of amorphous nickel tungstate (NiWO4) nanostructure and its application as a novel cathode material for supercapacitors. The effect of reaction temperature on the electrochemical properties of the NiWO4 electrode was studied, and results demonstrate that the material synthesized at 70 °C (NiW-70) has shown the highest specific capacitance of 586.2 F g(-1) at 0.5 A g(-1) in a three-electrode system. To achieve a high energy density, a NiW-70//activated carbon asymmetric supercapacitor is successfully assembled by use of NiW-70 and activated carbon as the cathode and anode, respectively, and then, its electrochemical performance is characterized by cyclic voltammetry and galvanostatic charge-discharge measurements. The results show that the assembled asymmetric supercapacitor can be cycled reversibly between 0 and 1.6 V with a high specific capacitance of 71.1 F g(-1) at 0.25 A g(-1), which can deliver a maximum energy density of 25.3 Wh kg(-1) at a power density of 200 W kg(-1). Furthermore, this asymmetric supercapacitor also presented an excellent, long cycle life along with 91.4% specific capacitance being retained after 5000 consecutive times of cycling.

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

    Science.gov (United States)

    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.

  4. Experimental and theoretical study on minimum achievable foil thickness during asymmetric rolling.

    Directory of Open Access Journals (Sweden)

    Delin Tang

    Full Text Available Parts produced by microforming are becoming ever smaller. Similarly, the foils required in micro-machines are becoming ever thinner. The asymmetric rolling technique is capable of producing foils that are thinner than those produced by the conventional rolling technique. The difference between asymmetric rolling and conventional rolling is the 'cross-shear' zone. However, the influence of the cross-shear zone on the minimum achievable foil thickness during asymmetric rolling is still uncertain. In this paper, we report experiments designed to understand this critical influencing factor on the minimum achievable thickness in asymmetric rolling. Results showed that the minimum achievable thickness of rolled foils produced by asymmetric rolling with a rolling speed ratio of 1.3 can be reduced to about 30% of that possible by conventional rolling technique. Furthermore, the minimum achievable thickness during asymmetric rolling could be correlated to the cross-shear ratio, which, in turn, could be related to the rolling speed ratio. From the experimental results, a formula to calculate the minimum achievable thickness was established, considering the parameters cross-shear ratio, friction coefficient, work roll radius, etc. in asymmetric rolling.

  5. Experimental and theoretical study on minimum achievable foil thickness during asymmetric rolling.

    Science.gov (United States)

    Tang, Delin; Liu, Xianghua; Song, Meng; Yu, Hailiang

    2014-01-01

    Parts produced by microforming are becoming ever smaller. Similarly, the foils required in micro-machines are becoming ever thinner. The asymmetric rolling technique is capable of producing foils that are thinner than those produced by the conventional rolling technique. The difference between asymmetric rolling and conventional rolling is the 'cross-shear' zone. However, the influence of the cross-shear zone on the minimum achievable foil thickness during asymmetric rolling is still uncertain. In this paper, we report experiments designed to understand this critical influencing factor on the minimum achievable thickness in asymmetric rolling. Results showed that the minimum achievable thickness of rolled foils produced by asymmetric rolling with a rolling speed ratio of 1.3 can be reduced to about 30% of that possible by conventional rolling technique. Furthermore, the minimum achievable thickness during asymmetric rolling could be correlated to the cross-shear ratio, which, in turn, could be related to the rolling speed ratio. From the experimental results, a formula to calculate the minimum achievable thickness was established, considering the parameters cross-shear ratio, friction coefficient, work roll radius, etc. in asymmetric rolling.

  6. In situ generation of N-Boc-protected alkenyl imines: controlling the E/Z geometry of alkenyl moieties in the Mukaiyama-Mannich reaction.

    Science.gov (United States)

    Bai, Jian-Fei; Sasagawa, Hajime; Yurino, Taiga; Kano, Taichi; Maruoka, Keiji

    2017-07-18

    Readily available Boc-protected Z-alkenyl aminals could be used as Z-alkenyl and E-alkenyl imine precursors under acidic conditions. In the Mukaiyama-Mannich reaction of Z-alkenyl Boc-aminals, the E/Z geometry of the products was controlled by the catalyst used. The present method was also applied to asymmetric Mukaiyama-Mannich reactions.

  7. N-Alkylation by Hydrogen Autotransfer Reactions.

    Science.gov (United States)

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed.

  8. Asymmetric synthesis II more methods and applications

    CERN Document Server

    Christmann, Mathias

    2012-01-01

    After the overwhelming success of 'Asymmetric Synthesis - The Essentials', narrating the colorful history of asymmetric synthesis, this is the second edition with latest subjects and authors. While the aim of the first edition was mainly to honor the achievements of the pioneers in asymmetric syntheses, the aim of this new edition was bringing the current developments, especially from younger colleagues, to the attention of students. The format of the book remained unchanged, i.e. short conceptual overviews by young leaders in their field including a short biography of the authors. The growing multidisciplinary research within chemistry is reflected in the selection of topics including metal catalysis, organocatalysis, physical organic chemistry, analytical chemistry, and its applications in total synthesis. The prospective reader of this book is a graduate or undergraduate student of advanced organic chemistry as well as the industrial chemist who wants to get a brief update on the current developments in th...

  9. Asymmetric Effects on Escape Rates of Bistable System

    International Nuclear Information System (INIS)

    Wang Canjun; Mei Dongcheng; Dai Zucheng

    2011-01-01

    The asymmetric effects on the escape rates from the stable states x ± in the bistable system are analyzed. The results indicate that the multiplicative noise and the additive noise always enhance the particle escape from stable states x ± of bistable. However, the asymmetric parameter r enhances the particle escape from stable state x + , and holds back the particle escape from stable state x - . (general)

  10. Diagnostic implications of asymmetrical mammographic patterns

    International Nuclear Information System (INIS)

    Asenjo, M.; Ania, B.J.

    1997-01-01

    To analyze the effect of asymmetrical mammographic patterns of the diagnosis of breast cancer. In a series of 6, 476 patients referred to a Breast Imaging Diagnosis Unit, we excluded males, women with previous breast surgery, and cases in which mammography was not performed, which left 5,203 women included. Each breast was classified according to one of four patterns of mammographic parenchymal density. Asymmetry was considered to exist when a patient's breasts had different patterns. Breast cancer was confirmed histologically in 282 (5.4%) women. The mammographic pattern was asymmetrical in 8% of the women with cancer and in 2% of the women without cancer (p<0.001). Fine-needle aspiration biopsy was performed in 78% and 96% (p=0.04), respectively, of the women with and without mammographic asymmetry who had neoplasms, and in 33% and 22% (p=0.02), respectively, of the women with and without mammographic asymmetry who did not have neoplasms. Asymmetrical mammographic pattern was four times more frequent in the women with breast cancer. This asymmetry decreased the frequency of needle biopsy in women with cancer, but increased the frequency of needle biopsy in women without cancer. (Author) 11 refs

  11. Hadron scattering in an asymmetric box

    International Nuclear Information System (INIS)

    Li Xin; Chen Ying; Meng Guozhan; Feng Xu; Gong Ming; He Song; Li Gang; Liu Chuan; Liu Yubin; Ma Jianping; Meng Xiangfei; Shen Yan; Zhang Jianbo

    2007-01-01

    We propose to study hadron-hadron scattering using lattice QCD in an asymmetric box which allows one to access more non-degenerate low-momentum modes for a given volume. The conventional Luescher's formula applicable in a symmetric box is modified accordingly. To illustrate the feasibility of this approach, pion-pion elastic scattering phase shifts in the I = 2, J = 0 channel are calculated within quenched approximation using improved gauge and Wilson fermion actions on anisotropic lattices in an asymmetric box. After the chiral and continuum extrapolation, we find that our quenched results for the scattering phase shifts in this channel are consistent with the experimental data when the three-momentum of the pion is below 300MeV. Agreement is also found when compared with previous theoretical results from lattice and other means. Moreover, with the usage of asymmetric volume, we are able to compute the scattering phases in the low-momentum range (pion three momentum less than about 350MeV in the center of mass frame) for over a dozen values of the pion three-momenta, much more than using the conventional symmetric box with comparable volume

  12. Uncovering the link between malfunctions in Drosophila neuroblast asymmetric cell division and tumorigenesis

    Directory of Open Access Journals (Sweden)

    Kelsom Corey

    2012-11-01

    Full Text Available Abstract Asymmetric cell division is a developmental process utilized by several organisms. On the most basic level, an asymmetric division produces two daughter cells, each possessing a different identity or fate. Drosophila melanogaster progenitor cells, referred to as neuroblasts, undergo asymmetric division to produce a daughter neuroblast and another cell known as a ganglion mother cell (GMC. There are several features of asymmetric division in Drosophila that make it a very complex process, and these aspects will be discussed at length. The cell fate determinants that play a role in specifying daughter cell fate, as well as the mechanisms behind setting up cortical polarity within neuroblasts, have proved to be essential to ensuring that neurogenesis occurs properly. The role that mitotic spindle orientation plays in coordinating asymmetric division, as well as how cell cycle regulators influence asymmetric division machinery, will also be addressed. Most significantly, malfunctions during asymmetric cell division have shown to be causally linked with neoplastic growth and tumor formation. Therefore, it is imperative that the developmental repercussions as a result of asymmetric cell division gone awry be understood.

  13. Oriented heavy ions and the choice of a cool compound nucleus reaction

    International Nuclear Information System (INIS)

    Aroumougame, R.; Gupta, R.K.

    1980-01-01

    Potential energy surfaces are calculated within the mechanism of fragmentation theory with a view to selecting the target-projectile combinations for producing new elements through cool compound nucleus formation. The orientation of the colliding nuclei is also included. It is shown that both the reaction partners of a cool compound nucleus, formed in either a central or a nearly central collision, should preferably be spherical and either nearly symmetric or extremely asymmetric. For reactions with deformed nuclei, it is suggested that polarised targets should be used. The calculations are illustrated for the compound nuclei 258 104 and 260 106. (author)

  14. Analysis of radial runout for symmetric and asymmetric HDD spindle motors with rotor eccentricity

    International Nuclear Information System (INIS)

    Kim, T.-J.; Kim, K.-T.; Hwang, S.-M.; Lee, S.-B.; Park, N.-G.

    2001-01-01

    Radial runout of disk drive spindle is one of the major limiting factors in achieving higher track densities in hard disk drives. Mechanical, magnetic and their coupled origins, such as unbalanced mass, reaction forces and magnetic forces, introduce radial runout of spindle motors. In this paper, radial magnetic forces are calculated with respect to the various rotor eccentricities using analytic method. Based on the results of the radial magnetic forces, the radial runout of the spindle motor is analyzed using finite element and transfer matrices. Results show that an asymmetric motor has a worse performance on unbalanced magnetic forces and radial runout when mechanical and magnetic coupling exists

  15. Using Agent Based Distillation to Explore Issues Related to Asymmetric Warfare

    Science.gov (United States)

    2009-10-01

    official definition of asymmetric warfare , considering that its use was redundant to irregular warfare [30]. 2 Such as the Lanchester Equations...RTP-MP-MSG-069 23 - 1 Using Agent Based Distillation to Explore Issues Related to Asymmetric Warfare Martin Adelantado, Jean-Michel Mathé...shows that both conventional and asymmetric warfare are characterised by nonlinear behaviours and that engagement is a Complex Adaptive System (CAS

  16. Total Synthesis of Ustiloxin D Utilizing an Ammonia-Ugi Reaction.

    Science.gov (United States)

    Brown, Aaron L; Churches, Quentin I; Hutton, Craig A

    2015-10-16

    Total synthesis of the highly functionalized cyclic peptide natural product, ustiloxin D, has been achieved in a convergent manner. Our strategy incorporates an asymmetric allylic alkylation to construct the tert-alkyl aryl ether linkage between the dopa and isoleucine residues. The elaborated β-hydroxydopa derivative is rapidly converted to a linear tripeptide through an ammonia-Ugi reaction. Subsequent cyclization and global deprotection affords ustiloxin D in six steps from a known β-hydroxydopa derivative.

  17. Statistical formulation of gravitational radiation reaction

    International Nuclear Information System (INIS)

    Schutz, B.F.

    1980-01-01

    A new formulation of the radiation-reaction problem is proposed, which is simpler than alternatives which have been used before. The new approach is based on the initial-value problem, uses approximations which need be uniformly valid only in compact regions of space-time, and makes no time-asymmetric assumptions (no a priori introduction of retarded potentials or outgoing-wave asymptotic conditions). It defines radiation reaction to be the expected evolution of a source obtained by averaging over a statistical ensemble of initial conditions. The ensemble is chosen to reflect one's complete lack of information (in real systems) about the initial data for the radiation field. The approach is applied to the simple case of a weak-field, slow-motion source in general relativity, where it yields the usual expressions for radiation reaction when the gauge is chosen properly. There is a discussion of gauge freedom, and another of the necessity of taking into account reaction corrections to the particle-conservation equation. The analogy with the second law of thermodynamics is very close, and suggests that the electromagnetic and thermodynamic arrows of time are the same. Because the formulation is based on the usual initial-value problem, it has no spurious ''runaway'' solutions

  18. Controllable asymmetric transmission via gap-tunable acoustic metasurface

    Science.gov (United States)

    Liu, Bingyi; Jiang, Yongyuan

    2018-04-01

    In this work, we utilize the acoustic gradient metasurface (AGM) of a bilayer configuration to realize the controllable asymmetric transmission. Relying on the adjustable gap between the two composing layers, the metasurface could switch from symmetric transmission to asymmetric transmission at a certain gap value. The underlying mechanism is attributed to the interference between the forward diffracted waves scattered by the surface bound waves at two air-AGM interfaces, which is apparently influenced by the interlayer distance. We further utilize the hybrid acoustic elements to construct the desired gradient metasurface with a tunable gap and validate the controllable asymmetric transmission with full-wave simulations. Our work provides the solution for actively controlling the transmission property of an acoustic element, which shows potential application in acoustic communication as a dynamic tunable acoustic diode.

  19. Examining the reaction of monetary policy to exchange rate changes: A nonlinear ARDL approach

    Science.gov (United States)

    Manogaran, Lavaneesvari; Sek, Siok Kun

    2017-04-01

    Previous studies showed the exchange rate changes can have significant impacts on macroeconomic performance. Over fluctuation of exchange rate may lead to economic instability. Hence, monetary policy rule tends to react to exchange rate changes. Especially, in emerging economies where the policy-maker tends to limit the exchange rate movement through interventions. In this study, we seek to investigate how the monetary policy rule reacts to exchange rate changes. The nonlinear autoregressive distributed lag (NARDL) model is applied to capture the asymmetric effect of exchange rate changes on monetary policy reaction function (interest rate). We focus the study in ASEAN5 countries (Indonesia, Malaysia, Philippines, Thailand and Singapore). The results indicated the existence of asymmetric effect of exchange rates changes on the monetary reaction function for all ASEAN5 countries in the long-run. Where, in majority of the cases the monetary policy is reacting to the appreciation and depreciation of exchange rate by raising the policy rate. This affirms the intervention of policymakers with the `fear of floating' behavior.

  20. Asymmetric Alkylation and Aldol Reactions of D-Mannitol-Derived Chiral Oxazolidin-2-one Derivatives

    International Nuclear Information System (INIS)

    Maeng, Yun Hee; Jun, Jong Gab

    2004-01-01

    In the preceding article, we have introduced a new chiral oxazolidin-2-one auxiliary (1) derived from a cheap Dmannitol, and demonstrated the chiral selectivity in alkylation, aldol reaction and β-lactam synthesis.1 The present work began with a search for useful chiral directing groups with which to control the chiral selectivity. Because the rigidity of cyclic structures contributes significantly to control of chirality,2 the 1,2:5,6-di-O-cyclohexylidene-Dmannitol (2) was used for the synthesis of oxazolidin-2-one chiral auxiliary (3) comparing the selectivity with the auxiliary (1) in alkylation and aldol reactions.

  1. Study on the output factors of asymmetrical rectangular electron beam field

    International Nuclear Information System (INIS)

    Chen Yinghai; Yang Yueqin; Ma Yuhong; Zheng Jin; Zou Lijuan

    2009-01-01

    Objective: To evaluate the variant regularity of the output factors of asymmetrical rectangular electron beam field. Methods: The output factors of three special fields with different applicators and energies were measured by ionization chamber method at different off-axis distances. Then deviations of the output factors between asymmetrical and symmetric rectangular fields were calculated. Results: The changes of output factor with different off-axis distances in asymmetrical rectangular fields were basically consistent with those in standard square fields with the same applicator. It revealed that the output factor of asymmetrical rectangular field was related with the off-axis ratio of standard square field. Applicator and field size did not show obvious influence on the output factor. Conclusions: The output factor changes of asymmetrical rectangular field are mainly correlated with the off-axis ratio of standard square field. The correction of the output factor is determined by the off-axis ratio changes in standard square field. (authors)

  2. Success Factors of Asymmetric Connections - Example of Large Slovenian Enterprises

    Directory of Open Access Journals (Sweden)

    Viktor Vračar

    2014-11-01

    Full Text Available More and more companies realize the fact that networking or partner collaborations, which are based on partner relations between companies, are essential for their long-term existence. In today’s global competitive environment each company is included at least in some different connections. Very common connections occur between large and smaller enterprises, where the so called asymmetric connections occur, which may be understood as the ability of one organisation to establish power, influence and control over the other organisation and its resources. According to numerous statements, the connections between enterprises are very frequently uneffectivenessful, with opinions on the optimal nature of asymmetric connections being quite common as well, whereby it is, as a rule, a synergic complementing of missing content for both partners. To verify the thesis, that companies achieve more competitiveness and effectiveness through connections, whereby the so called asymmetric connections are common, a structural model of the evolution of asymmetric connection has been developed, which connects the theoretically identified factors and all dependent concepts of competitiveness, efficiency and effectiveness. The empirical research also attempts to further expose the factors of asymmetric connections, which affect efficiency and effectiveness of the connected enterprises.

  3. Symmetrization of the beam-beam interaction in an asymmetric collider

    International Nuclear Information System (INIS)

    Chin, Y.H.

    1990-07-01

    This paper studies the idea of symmetrizing both the lattice and the beams of an asymmetric collider, and discusses why this regime should be within the parametric reach of the design in order to credibly ensure its performance. Also examined is the effectiveness of a simple compensation method using the emittance as a free parameter and that it does not work in all cases. At present, when there are no existing asymmetric colliders, it seems prudent to design an asymmetric collider so as to be similar to a symmetric one (without relying on a particular theory of the asymmetric beam-beam interaction that has not passed tests of fidelity). Nevertheless, one must allow for the maximum possible flexibility and freedom in adjusting those parameters that affect luminosity. Such a parameter flexibility will be essential in tuning the collider to the highest luminosity

  4. Force on an Asymmetric Capacitor

    National Research Council Canada - National Science Library

    Bahder, Thomas

    2003-01-01

    .... 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...

  5. P-chiral 1-phosphanorbornenes: from asymmetric phospha-Diels-Alder reactions towards ligand design and functionalisation.

    Science.gov (United States)

    Möller, Tobias; Wonneberger, Peter; Sárosi, Menyhárt B; Coburger, Peter; Hey-Hawkins, Evamarie

    2016-02-07

    The principle of stereotopic face differentiation was successfully applied to 2H-phospholes which undergo a very efficient and highly stereoselective Diels-Alder reaction giving phosphorus-chiral 1-phosphanorbornenes with up to 87% yield. The observed reaction pathway has been supported by theoretical calculations showing that the cycloaddition reaction between 2H-phosphole 3a and the dienophile (5R)-(-)-menthyloxy-2(5H)-furanone (8) is of normal electron demand. Optically pure phosphanes were obtained by separation of the single diastereomers and subsequent desulfurisation of the sulfur-protected phosphorus atom. Finally, divergent ligand synthesis is feasible by reduction of the chiral auxiliary, subsequent stereospecific intramolecular Michael addition, and various functionalisations of the obtained key compound 13a. Furthermore, the unique structural properties of phospanorbornenes are presented and compared to those of phosphanorbornanes.

  6. Pauli blocking and medium effects in nucleon knockout reactions

    International Nuclear Information System (INIS)

    Bertulani, C. A.; De Conti, C.

    2010-01-01

    We study medium modifications of the nucleon-nucleon (NN) cross sections and their influence on the nucleon knockout reactions. Using the eikonal approximation, we compare the results obtained with free NN cross sections with those obtained with a purely geometrical treatment of Pauli blocking and with NN obtained with more elaborated Dirac-Bruecker methods. The medium effects are parametrized in terms of the baryon density. We focus on symmetric nuclear matter, although the geometrical Pauli blocking also allows for the treatment of asymmetric nuclear matter. It is shown that medium effects can change the nucleon knockout cross sections and momentum distributions up to 10% in the energy range E lab =50-300 MeV/nucleon. The effect is more evident in reactions involving halo nuclei.

  7. Asymmetric synthesis of cyclo-archaeol and ß-glucosyl cyclo-archaeol

    NARCIS (Netherlands)

    Ferrer, C.; Fodran, P.; Barroso, S.; Gibson, R.; Hopmans, E.C.; Sinninghe Damsté, J.S.; Schouten, S.; Minnaard, A.J.

    2013-01-01

    An efficient asymmetric synthesis of cyclo-archaeol and beta-glucosyl cyclo-archaeol is presented employing catalytic asymmetric conjugate addition and catalytic epoxide ring opening as the key steps. Their occurrence in deep sea hydrothermal vents has been confirmed by chromatographic comparison

  8. Asymmetric Damage Segregation Constitutes an Emergent Population-Level Stress Response

    DEFF Research Database (Denmark)

    Vedel, Søren; Nunns, Harry; Košmrlj, Andrej

    2016-01-01

    Asymmetric damage segregation (ADS) is a mechanism for increasing population fitness through non-random, asymmetric partitioning of damaged macromolecules at cell division. ADS has been reported across multiple organisms, though the measured effects on fitness of individuals are often small. Here...

  9. Asymmetric-cut variable-incident-angle monochromator.

    Science.gov (United States)

    Smither, R K; Graber, T J; Fernandez, P B; Mills, D M

    2012-03-01

    A novel asymmetric-cut variable-incident-angle monochromator was constructed and tested in 1997 at the Advanced Photon Source of Argonne National Laboratory. The monochromator was originally designed as a high heat load monochromator capable of handling 5-10 kW beams from a wiggler source. This was accomplished by spreading the x-ray beam out on the surface an asymmetric-cut crystal and by using liquid metal cooling of the first crystal. The monochromator turned out to be a highly versatile monochromator that could perform many different types of experiments. The monochromator consisted of two 18° asymmetrically cut Si crystals that could be rotated about 3 independent axes. The first stage (Φ) rotates the crystal around an axis perpendicular to the diffraction plane. This rotation changes the angle of the incident beam with the surface of the crystal without changing the Bragg angle. The second rotation (Ψ) is perpendicular to the first and is used to control the shape of the beam footprint on the crystal. The third rotation (Θ) controls the Bragg angle. Besides the high heat load application, the use of asymmetrically cut crystals allows one to increase or decrease the acceptance angle for crystal diffraction of a monochromatic x-ray beam and allows one to increase or decrease the wavelength bandwidth of the diffraction of a continuum source like a bending-magnet beam or a normal x-ray-tube source. When the monochromator is used in the doubly expanding mode, it is possible to expand the vertical size of the double-diffracted beam by a factor of 10-15. When this was combined with a bending magnet source, it was possible to generate an 8 keV area beam, 16 mm wide by 26 mm high with a uniform intensity and parallel to 1.2 arc sec that could be applied in imaging experiments.

  10. Modulational Instability in Linearly Coupled Asymmetric Dual-Core Fibers

    Directory of Open Access Journals (Sweden)

    Arjunan Govindarajan

    2017-06-01

    Full Text Available We investigate modulational instability (MI in asymmetric dual-core nonlinear directional couplers incorporating the effects of the differences in effective mode areas and group velocity dispersions, as well as phase- and group-velocity mismatches. Using coupled-mode equations for this system, we identify MI conditions from the linearization with respect to small perturbations. First, we compare the MI spectra of the asymmetric system and its symmetric counterpart in the case of the anomalous group-velocity dispersion (GVD. In particular, it is demonstrated that the increase of the inter-core linear-coupling coefficient leads to a reduction of the MI gain spectrum in the asymmetric coupler. The analysis is extended for the asymmetric system in the normal-GVD regime, where the coupling induces and controls the MI, as well as for the system with opposite GVD signs in the two cores. Following the analytical consideration of the MI, numerical simulations are carried out to explore nonlinear development of the MI, revealing the generation of periodic chains of localized peaks with growing amplitudes, which may transform into arrays of solitons.

  11. An N-Linked Bidentate Phosphoramidite Ligand (N-Me-BIPAM for Rhodium-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Ketones

    Directory of Open Access Journals (Sweden)

    Norio Miyaura

    2012-12-01

    Full Text Available A new bidentate phosphoramidite (N-Me-BIPAM based on Shibasaki’s N-linked BINOL was synthesized. This ligand appears to be highly effective for rhodium-catalyzed asymmetric conjugated addition of arylboronic acids to α,β-unsaturated enones. The reaction of ortho-substituted arylboronic acid with acyclic and cyclic enones provides the corresponding products in good yields and enantioselectivities.

  12. Modes of reaction front propagation and end-gas combustion of hydrogen/air mixtures in a closed chamber

    KAUST Repository

    Shi, Xian

    2017-01-05

    Modes of reaction front propagation and end-gas combustion of hydrogen/air mixtures in a closed chamber are numerically investigated using an 1-D unsteady, shock-capturing, compressible and reacting flow solver. Different combinations of reaction front propagation and end-gas combustion modes are observed, i.e., 1) deflagration without end-gas combustion, 2) deflagration to end-gas autoignition, 3) deflagration to end-gas detonation, 4) developing or developed detonation, occurring in the sequence of increasing initial temperatures. Effects of ignition location and chamber size are evaluated: the asymmetric ignition is found to promote the reactivity of unburnt mixture compared to ignitions at center/wall, due to additional heating from asymmetric pressure waves. End-gas combustion occurs earlier in smaller chambers, where end-gas temperature rise due to compression heating from the deflagration is faster. According to the ξ−ε regime diagram based on Zeldovich theory, modes of reaction front propagation are primarily determined by reactivity gradients introduced by initial ignition, while modes of end-gas combustion are influenced by the total amount of unburnt mixture at the time when autoignition occurs. A transient reactivity gradient method is provided and able to capture the occurrence of detonation.

  13. Modes of reaction front propagation and end-gas combustion of hydrogen/air mixtures in a closed chamber

    KAUST Repository

    Shi, Xian; Ryu, Je Ir; Chen, Jyh-Yuan; Dibble, Robert W.

    2017-01-01

    Modes of reaction front propagation and end-gas combustion of hydrogen/air mixtures in a closed chamber are numerically investigated using an 1-D unsteady, shock-capturing, compressible and reacting flow solver. Different combinations of reaction front propagation and end-gas combustion modes are observed, i.e., 1) deflagration without end-gas combustion, 2) deflagration to end-gas autoignition, 3) deflagration to end-gas detonation, 4) developing or developed detonation, occurring in the sequence of increasing initial temperatures. Effects of ignition location and chamber size are evaluated: the asymmetric ignition is found to promote the reactivity of unburnt mixture compared to ignitions at center/wall, due to additional heating from asymmetric pressure waves. End-gas combustion occurs earlier in smaller chambers, where end-gas temperature rise due to compression heating from the deflagration is faster. According to the ξ−ε regime diagram based on Zeldovich theory, modes of reaction front propagation are primarily determined by reactivity gradients introduced by initial ignition, while modes of end-gas combustion are influenced by the total amount of unburnt mixture at the time when autoignition occurs. A transient reactivity gradient method is provided and able to capture the occurrence of detonation.

  14. Effects of asymmetrical stance and movement on body rotation in pushing.

    Science.gov (United States)

    Lee, Yun-Ju; Aruin, Alexander S

    2015-01-21

    Pushing objects in the presence of body asymmetries could increase the risk of back injury. Furthermore, when the object is heavy, it could exacerbate the effects induced by asymmetrical posture. We investigated how the use of asymmetrical posture and/or upper extremity movement affect vertical torque (Tz) and center of pressure (COP) displacement during pushing. Ten healthy volunteers were instructed to push objects of three different weights using two hands (symmetrical hand use) or one hand (asymmetrical hand use) while standing in symmetrical or asymmetrical foot-positions. The peak values of Tz and COP displacement in the medial-lateral direction (COPML) were analyzed. In cases of isolated asymmetry, changes in the Tz were mainly linked with effects of hand-use whereas effects of foot-position dominated changes in the COPML displacement. In cases of a combined asymmetry, the magnitudes of both Tz and COPML were additive when asymmetrical hand-use and foot-position induced the rotation of the lower and upper body in the same direction or subtractive when asymmetries resulted in the rotation of the body segments in the opposite directions. Moreover, larger Tz and COP displacements were seen when pushing the heavy weight. The results point out the importance of using Tz and COPML to describe the isolated or combined effects of asymmetrical upper extremity movement and asymmetrical posture on body rotation during pushing. Furthermore, it suggests that a proper combination of unilateral arm movement and foot placements could help to reduce body rotation even when pushing heavy objects. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Project financing versus corporate financing under asymmetric information

    OpenAIRE

    Anton Miglo

    2008-01-01

    In recent years financing through the creation of an independent project company or financing by non-recourse debt has become an important part of corporate decisions. Shah and Thakor (JET, 1987) argue that project financing can be optimal when asymmetric information exists between firm's insiders and market participants. In contrast to that paper, we provide an asymmetric information argument for project financing without relying on corporate taxes, costly information production or an assump...

  16. Asymmetric Shaped-Pattern Synthesis for Planar Antenna Arrays

    Directory of Open Access Journals (Sweden)

    T. M. Bruintjes

    2016-01-01

    Full Text Available A procedure to synthesize asymmetrically shaped beam patterns is developed for planar antenna arrays. As it is based on the quasi-analytical method of collapsed distributions, the main advantage of this procedure is the ability to realize a shaped (null-free region with very low ripple. Smooth and asymmetrically shaped regions can be used for Direction-of-Arrival estimation and subsequently for efficient tracking with a single output (fully analog beamformer.

  17. Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

    Science.gov (United States)

    Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

    2015-09-23

    Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

  18. Enantioselective organocatalyzed Oxa-Michael-Aldol cascade reactions: Construction of chiral 4H-chromenes with a trifluoromethylated tetrasubstituted carbon stereocenter

    KAUST Repository

    Zhang, Jing

    2015-03-13

    The first organocatalytic asymmetric synthesis of 4H-chromenes bearing a trifluoromethylated tetrasubstituted carbon center is presented. Chiral secondary amines promote the oxa-Michael-aldol cascade reaction between alkynals and 2-trifluoroacetylphenols via iminium-allenamine activation to produce pharmaceutically important heterocycles with excellent enantioselectivities. The proposed reaction can be scaled-up easily with maintenance of the excellent enantioselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Asymmetric collider

    International Nuclear Information System (INIS)

    Bharadwaj, V.; Colestock, P.; Goderre, G.; Johnson, D.; Martin, P.; Holt, J.; Kaplan, D.

    1993-01-01

    The study of CP violation in beauty decay is one of the key challenges facing high energy physics. Much work has not yielded a definitive answer how this study might best be performed. However, one clear conclusion is that new accelerator facilities are needed. Proposals include experiments at asymmetric electron-positron colliders and in fixed-target and collider modes at LHC and SSC. Fixed-target and collider experiments at existing accelerators, while they might succeed in a first observation of the effect, will not be adequate to study it thoroughly. Giomataris has emphasized the potential of a new approach to the study of beauty CP violation: the asymmetric proton collider. Such a collider might be realized by the construction of a small storage ring intersecting an existing or soon-to-exist large synchrotron, or by arranging collisions between a large synchrotron and its injector. An experiment at such a collider can combine the advantages of fixed-target-like spectrometer geometry, facilitating triggering, particle identification and the instrumentation of a large acceptance, while the increased √s can provide a factor > 100 increase in beauty-production cross section compared to Tevatron or HERA fixed-target. Beams crossing at a non-zero angle can provide a small interaction region, permitting a first-level decay-vertex trigger to be implemented. To achieve large √s with a large Lorentz boost and high luminosity, the most favorable venue is the high-energy booster (HEB) at the SSC Laboratory, though the CERN SPS and Fermilab Tevatron are also worth considering

  20. An Evolving Asymmetric Game for Modeling Interdictor-Smuggler Problems

    Science.gov (United States)

    2016-06-01

    ASYMMETRIC GAME FOR MODELING INTERDICTOR-SMUGGLER PROBLEMS by Richard J. Allain June 2016 Thesis Advisor: David L. Alderson Second Reader: W...DATES COVERED Master’s thesis 4. TITLE AND SUBTITLE AN EVOLVING ASYMMETRIC GAME FOR MODELING INTERDICTOR- SMUGGLER PROBLEMS 5. FUNDING NUMBERS 6...NAVAL POSTGRADUATE SCHOOL MONTEREY, CALIFORNIA THESIS Approved for public release; distribution is unlimited AN EVOLVING

  1. Asymmetric Penning trap coherent states

    International Nuclear Information System (INIS)

    Contreras-Astorga, Alonso; Fernandez, David J.

    2010-01-01

    By using a matrix technique, which allows to identify directly the ladder operators, the coherent states of the asymmetric Penning trap are derived as eigenstates of the appropriate annihilation operators. They are compared with those obtained through the displacement operator method.

  2. Asymmetric threat data mining and knowledge discovery

    Science.gov (United States)

    Gilmore, John F.; Pagels, Michael A.; Palk, Justin

    2001-03-01

    Asymmetric threats differ from the conventional force-on- force military encounters that the Defense Department has historically been trained to engage. Terrorism by its nature is now an operational activity that is neither easily detected or countered as its very existence depends on small covert attacks exploiting the element of surprise. But terrorism does have defined forms, motivations, tactics and organizational structure. Exploiting a terrorism taxonomy provides the opportunity to discover and assess knowledge of terrorist operations. This paper describes the Asymmetric Threat Terrorist Assessment, Countering, and Knowledge (ATTACK) system. ATTACK has been developed to (a) data mine open source intelligence (OSINT) information from web-based newspaper sources, video news web casts, and actual terrorist web sites, (b) evaluate this information against a terrorism taxonomy, (c) exploit country/region specific social, economic, political, and religious knowledge, and (d) discover and predict potential terrorist activities and association links. Details of the asymmetric threat structure and the ATTACK system architecture are presented with results of an actual terrorist data mining and knowledge discovery test case shown.

  3. Gordoni koolitused / Steve Emmons

    Index Scriptorium Estoniae

    Emmons, Steve

    2006-01-01

    Gordoni metodoloogia Master Trainer rääkis oma Eestis toimunud koolitusel põhilistest suhtlemisvigadest, Gordoni koolitustel õpitavast ning suhtlemisoskuse olulisusest organisatsiooni töökliimale

  4. Designing 3D highly ordered nanoporous CuO electrodes for high-performance asymmetric supercapacitors.

    Science.gov (United States)

    Moosavifard, Seyyed E; El-Kady, Maher F; Rahmanifar, Mohammad S; Kaner, Richard B; Mousavi, Mir F

    2015-03-04

    The increasing demand for energy has triggered tremendous research efforts for the development of lightweight and durable energy storage devices. Herein, we report a simple, yet effective, strategy for high-performance supercapacitors by building three-dimensional pseudocapacitive CuO frameworks with highly ordered and interconnected bimodal nanopores, nanosized walls (∼4 nm) and large specific surface area of 149 m(2) g(-1). This interesting electrode structure plays a key role in providing facilitated ion transport, short ion and electron diffusion pathways and more active sites for electrochemical reactions. This electrode demonstrates excellent electrochemical performance with a specific capacitance of 431 F g(-1) (1.51 F cm(-2)) at 3.5 mA cm(-2) and retains over 70% of this capacitance when operated at an ultrafast rate of 70 mA cm(-2). When this highly ordered CuO electrode is assembled in an asymmetric cell with an activated carbon electrode, the as-fabricated device demonstrates remarkable performance with an energy density of 19.7 W h kg(-1), power density of 7 kW kg(-1), and excellent cycle life. This work presents a new platform for high-performance asymmetric supercapacitors for the next generation of portable electronics and electric vehicles.

  5. Holding-time-aware asymmetric spectrum allocation in virtual optical networks

    Science.gov (United States)

    Lyu, Chunjian; Li, Hui; Liu, Yuze; Ji, Yuefeng

    2017-10-01

    Virtual optical networks (VONs) have been considered as a promising solution to support current high-capacity dynamic traffic and achieve rapid applications deployment. Since most of the network services (e.g., high-definition video service, cloud computing, distributed storage) in VONs are provisioned by dedicated data centers, needing different amount of bandwidth resources in both directions, the network traffic is mostly asymmetric. The common strategy, symmetric provisioning of traffic in optical networks, leads to a waste of spectrum resources in such traffic patterns. In this paper, we design a holding-time-aware asymmetric spectrum allocation module based on SDON architecture and an asymmetric spectrum allocation algorithm based on the module is proposed. For the purpose of reducing spectrum resources' waste, the algorithm attempts to reallocate the idle unidirectional spectrum slots in VONs, which are generated due to the asymmetry of services' bidirectional bandwidth. This part of resources can be exploited by other requests, such as short-time non-VON requests. We also introduce a two-dimensional asymmetric resource model for maintaining idle spectrum resources information of VON in spectrum and time domains. Moreover, a simulation is designed to evaluate the performance of the proposed algorithm, and results show that our proposed asymmetric spectrum allocation algorithm can improve the resource waste and reduce blocking probability.

  6. Asymmetric Price Transmission in Indonesia's Wheat Flour Market

    OpenAIRE

    Varela, Gonzalo J.; Taniguchi, Kiyoshi

    2014-01-01

    Data indicate that its domestic price in Indonesia has been increasing regardless of movements in the international price of wheat. A test for asymmetric price transmission from international wheat to domestic wheat flour markets is conducted using an error correction model and find the presence of asymmetric price transmission. The upward adjustment in the domestic price of wheat flour is much faster than its adjustment downward when it deviates from long-run equilibrium. Our results are rob...

  7. Coulomb effects in isobaric cold fission from reactions 233U(nth,f), 235U(nth,f),239Pu(nth,f) and 252Cf(sf)

    International Nuclear Information System (INIS)

    Montoya, Modesto

    2013-01-01

    The Coulomb effect hypothesis, formerly used to interpret fluctuations in the curve of maximal total kinetic energy as a function of light fragment mass in reactions 233 U(n th ,f), 235 U(n th ,f) and 239 Pu(n th ,f), is confirmed in high kinetic energy as well as in low excitation energy windows, respectively. Data from reactions 233 U(n th ,f), 235 U(n th ,f), 239 Pu(n th ,f) and 252 Cf(sf) show that, between two isobaric fragmentations with similar Q-values, the more asymmetric charge split reaches the higher value of total kinetic energy. Moreover, in isobaric charge splits with different Q-values, similar preference for asymmetrical fragmentations is observed in low excitation energy windows. (author).

  8. Selectivity in heavy ion transfer reactions

    International Nuclear Information System (INIS)

    Boucenna, A.

    1989-01-01

    One-two-and three-nucleon stripping reactions induced by 480 MeV 12 C and by 793 MeV 16 O have been studied on 12 C, 16 O, 28 Si, 40 Ca, and 54 Fe targets. Discrete levels are fed with cross sections up to 1 mb/sr for d-transfer reactions and one and two orders of magnitude less for 2p- and 3 He-transfers, respectively. These reactions are governed by two selection rules contained in the semi-classical model of Brink: i) Large orbital final momentum states are selectively populated and ii) The most highly populated states correspond to no-flip transitions. Two-proton transfer reactions induced by 112 MeV 12 C on even Ni and Zn isotopes are found to be less selective than two-neutron transfer reactions induced by the same projectile on the same targets in a similar incident energy range. The additional collective aspects observed in the two-proton transfers are examined in view of a semiphenomenological model of two quasi-particles coupled to a triaxial asymmetric rotor. The energy of excited states is well reproduced by simple shell model calculations. Such estimates are useful in proposing spins of newly observed states, especially as the shapes of the measured angular distributions are independant of the final spin of the residual nucleus. The experimental results of two-proton and two-neutron stripping reactions and the simple shell model allow an estimate of two-body matrix elements describing the nucleon-nucleon interaction and of the Coulomb energy [fr

  9. Asymmetrical Capacitors for Propulsion and the ISR Asymmetrical Capacitator Thruster, Experimental Results and Improved Designs

    Science.gov (United States)

    Canning, Francis; Winet, Ed; Ice, Bob; Melcher, Cory; Pesavento, Phil; Holmes, Alan; Butler, Carey; Cole, John; Campbell, Jonathan

    2004-01-01

    The outline of this viewgraph presentation on asymmetrical capacitor thruster development includes: 1) Test apparatus; 2) Devices tested; 3) Circuits used; 4) Data collected (Time averaged, Time resolved); 5) Patterns observed; 6) Force calculation; 7) Electrostatic modeling; 8) Understand it all.

  10. From design to manufacturing of asymmetric teeth gears using computer application

    Science.gov (United States)

    Suciu, F.; Dascalescu, A.; Ungureanu, M.

    2017-05-01

    The asymmetric cylindrical gears, with involutes teeth profiles having different base circle diameters, are nonstandard gears, used with the aim to obtain better function parameters for the active profile. We will expect that the manufacturing of these gears became possible only after the design and realization of some specific tools. The paper present how the computer aided design and applications developed in MATLAB, for obtain the geometrical parameters, in the same time for calculation some functional parameters like stress and displacements, transmission error, efficiency of the gears and the 2D models, generated with AUTOLISP applications, are used for computer aided manufacturing of asymmetric gears with standard tools. So the specific tools considered one of the disadvantages of these gears are not necessary and implicitly the expected supplementary costs are reduced. The calculus algorithm established for the asymmetric gear design application use the „direct design“ of the spur gears. This method offers the possibility of determining first the parameters of the gears, followed by the determination of the asymmetric gear rack’s parameters, based on those of the gears. Using original design method and computer applications have been determined the geometrical parameters, the 2D and 3D models of the asymmetric gears and on the base of these models have been manufacturing on CNC machine tool asymmetric gears.

  11. Totally Asymmetric Limit for Models of Heat Conduction

    Science.gov (United States)

    De Carlo, Leonardo; Gabrielli, Davide

    2017-08-01

    We consider one dimensional weakly asymmetric boundary driven models of heat conduction. In the cases of a constant diffusion coefficient and of a quadratic mobility we compute the quasi-potential that is a non local functional obtained by the solution of a variational problem. This is done using the dynamic variational approach of the macroscopic fluctuation theory (Bertini et al. in Rev Mod Phys 87:593, 2015). The case of a concave mobility corresponds essentially to the exclusion model that has been discussed in Bertini et al. (J Stat Mech L11001, 2010; Pure Appl Math 64(5):649-696, 2011; Commun Math Phys 289(1):311-334, 2009) and Enaud and Derrida (J Stat Phys 114:537-562, 2004). We consider here the convex case that includes for example the Kipnis-Marchioro-Presutti (KMP) model and its dual (KMPd) (Kipnis et al. in J Stat Phys 27:6574, 1982). This extends to the weakly asymmetric regime the computations in Bertini et al. (J Stat Phys 121(5/6):843-885, 2005). We consider then, both microscopically and macroscopically, the limit of large externalfields. Microscopically we discuss some possible totally asymmetric limits of the KMP model. In one case the totally asymmetric dynamics has a product invariant measure. Another possible limit dynamics has instead a non trivial invariant measure for which we give a duality representation. Macroscopically we show that the quasi-potentials of KMP and KMPd, which are non local for any value of the external field, become local in the limit. Moreover the dependence on one of the external reservoirs disappears. For models having strictly positive quadratic mobilities we obtain instead in the limit a non local functional having a structure similar to the one of the boundary driven asymmetric exclusion process.

  12. Best Speed Fit EDF Scheduling for Performance Asymmetric Multiprocessors

    Directory of Open Access Journals (Sweden)

    Peng Wu

    2017-01-01

    Full Text Available In order to improve the performance of a real-time system, asymmetric multiprocessors have been proposed. The benefits of improved system performance and reduced power consumption from such architectures cannot be fully exploited unless suitable task scheduling and task allocation approaches are implemented at the operating system level. Unfortunately, most of the previous research on scheduling algorithms for performance asymmetric multiprocessors is focused on task priority assignment. They simply assign the highest priority task to the fastest processor. In this paper, we propose BSF-EDF (best speed fit for earliest deadline first for performance asymmetric multiprocessor scheduling. This approach chooses a suitable processor rather than the fastest one, when allocating tasks. With this proposed BSF-EDF scheduling, we also derive an effective schedulability test.

  13. Gravity-induced asymmetric distribution of a plant growth hormone

    Science.gov (United States)

    Bandurski, R. S.; Schulze, A.; Momonoki, Y.

    1984-01-01

    Dolk (1936) demonstrated that gravistimulation induced an asymmetric distribution of auxin in a horizontally-placed shoot. An attempt is made to determine where and how that asymmetry arises, and to demonstrate that the endogenous auxin, indole-3-acetic acid, becomes asymmetrically distributed in the cortical cells of the Zea mays mesocotyl during 3 min of geostimulation. Further, indole-3-acetic acid derived by hydrolysis of an applied transport form of the hormone, indole-3-acetyl-myo-inositol, becomes asymmetrically distributed within 15 min of geostimulus time. From these and prior data is developed a working theory that the gravitational stimulus induces a selective leakage, or secretion, of the hormone from the vascular tissue to the cortical cells of the mesocotyl.

  14. Asymmetric acoustic transmission in multiple frequency bands

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Hong-xiang, E-mail: jsdxshx@ujs.edu.cn [Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013 (China); Laboratory of Modern Acoustics, Institute of Acoustics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China); State Key Laboratory of Acoustics, Institute of Acoustics, Chinese Academy of Sciences, Beijing 100190 (China); Yuan, Shou-qi, E-mail: Shouqiy@ujs.edu.cn [Research Center of Fluid Machinery Engineering and Technology, Jiangsu University, Zhenjiang 212013 (China); Zhang, Shu-yi [Laboratory of Modern Acoustics, Institute of Acoustics, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093 (China)

    2015-11-23

    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.

  15. Asymmetric acoustic transmission in multiple frequency bands

    International Nuclear Information System (INIS)

    Sun, Hong-xiang; Yuan, Shou-qi; Zhang, Shu-yi

    2015-01-01

    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

  16. Stable walking with asymmetric legs

    International Nuclear Information System (INIS)

    Merker, Andreas; Rummel, Juergen; Seyfarth, Andre

    2011-01-01

    Asymmetric leg function is often an undesired side-effect in artificial legged systems and may reflect functional deficits or variations in the mechanical construction. It can also be found in legged locomotion in humans and animals such as after an accident or in specific gait patterns. So far, it is not clear to what extent differences in the leg function of contralateral limbs can be tolerated during walking or running. Here, we address this issue using a bipedal spring-mass model for simulating walking with compliant legs. With the help of the model, we show that considerable differences between contralateral legs can be tolerated and may even provide advantages to the robustness of the system dynamics. A better understanding of the mechanisms and potential benefits of asymmetric leg operation may help to guide the development of artificial limbs or the design novel therapeutic concepts and rehabilitation strategies.

  17. Polarization dependent switching of asymmetric nanorings with a circular field

    Directory of Open Access Journals (Sweden)

    Nihar R. Pradhan

    2016-01-01

    Full Text Available We experimentally investigated the switching from onion to vortex states in asymmetric cobalt nanorings by an applied circular field. An in-plane field is applied along the symmetric or asymmetric axis of the ring to establish domain walls (DWs with symmetric or asymmetric polarization. A circular field is then applied to switch from the onion state to the vortex state, moving the DWs in the process. The asymmetry of the ring leads to different switching fields depending on the location of the DWs and direction of applied field. For polarization along the asymmetric axis, the field required to move the DWs to the narrow side of the ring is smaller than the field required to move the DWs to the larger side of the ring. For polarization along the symmetric axis, establishing one DW in the narrow side and one on the wide side, the field required to switch to the vortex state is an intermediate value.

  18. [Combined orthodontic-orthoganthic surgery to treat asymmetric mandibular excess malocclusions].

    Science.gov (United States)

    Li, Xiao-Bing; Chen, Song; Chen, Yang-Xi; Li, Jun

    2005-06-01

    To discuss the skeletal and dentoalveolar characteristics of asymmetric mandibular excess malocclusions and to discuss the procedures of combined orthodontic-orthonganthic surgery treatments of asymmetric mandibular excess malocclusions. 25 cases treated by combined orthodontic-orthognathic surgery treatments were reviewed to find out the specialties of this kind of therapy. The asymmetric of mandible presents anterior and posterior teeth tipped both sagitally and horizontally, as well as upper and lower jaws incompatibility. The pre-surgical orthodontic treatments included decomposition of anterior and posterior teeth, leveling and aligning the teeth etc. The post-surgical orthodontic treatments were to detail the occlusions. The patients all got functional and aesthetic good results after the combined orthodontic-orthognathic surgery treatments. The asymmetric mandibular excess affects the harmony of the face badly, and the correction of it must be carried out by the combined orthodontic-orthognathic surgery treatments. The pre- and post-surgical orthodontic treatments are the key stages to make the skeletal corrections stable.

  19. High Current Ionic Diode Using Homogeneously Charged Asymmetric Nanochannel Network Membrane.

    Science.gov (United States)

    Choi, Eunpyo; Wang, Cong; Chang, Gyu Tae; Park, Jungyul

    2016-04-13

    A high current ionic diode is achieved using an asymmetric nanochannel network membrane (NCNM) constructed by soft lithography and in situ self-assembly of nanoparticles with uniform surface charge. The asymmetric NCNM exhibits high rectified currents without losing a rectification ratio because of its ionic selectivity gradient and differentiated electrical conductance. Asymmetric ionic transport is analyzed with diode-like I-V curves and visualized via fluorescent dyes, which is closely correlated with ionic selectivity and ion distribution according to variation of NCNM geometries.

  20. Design of activated carbon/activated carbon asymmetric capacitors

    Science.gov (United States)

    Piñeiro-Prado, Isabel; Salinas-Torres, David; Ruiz Rosas, Ramiro; Morallon, Emilia; Cazorla-Amoros, Diego

    2016-03-01

    Supercapacitors are energy storage devices that offer a high power density and a low energy density in comparison with batteries. Their limited energy density can be overcome by using asymmetric configuration in mass electrodes, where each electrode works within their maximum available potential window, rendering the maximum voltage output of the system. Such asymmetric capacitors must be optimized through careful electrochemical characterization of the electrodes for accurate determination of the capacitance and the potential stability limits. The results of the characterization are then used for optimizing mass ratio of the electrodes from the balance of stored charge. The reliability of the design largely depends on the approach taken for the electrochemical characterization. Therefore, the performance could be lower than expected and even the system could break down, if a well thought out procedure is not followed. In this work, a procedure for the development of asymmetric supercapacitors based on activated carbons is detailed. Three activated carbon materials with different textural properties and surface chemistry have been systematically characterized in neutral aqueous electrolyte. The asymmetric configuration of the masses of both electrodes in the supercapacitor has allowed to cover a higher potential window, resulting in an increase of the energy density of the three devices studied when compared with the symmetric systems, and an improved cycle life.

  1. Design of activated carbon/activated carbon asymmetric capacitors

    Directory of Open Access Journals (Sweden)

    Isabel ePiñeiro-Prado

    2016-03-01

    Full Text Available Supercapacitors are energy storage devices that offer a high power density and a low energy density in comparison with batteries. Their limited energy density can be overcome by using asymmetric configuration in mass electrodes, where each electrode works within their maximum available potential window, rendering the maximum voltage output of the system. Such asymmetric capacitors must be optimized through careful electrochemical characterization of the electrodes for accurate determination of the capacitance and the potential stability limits. The results of the characterization are then used for optimizing mass ratio of the electrodes from the balance of stored charge. The reliability of the design largely depends on the approach taken for the electrochemical characterization. Therefore, the performance could be lower than expected and even the system could break down, if a well thought out procedure is not followed.In this work, a procedure for the development of asymmetric supercapacitors based on activated carbons is detailed. Three activated carbon materials with different textural properties and surface chemistry have been systematically characterized in neutral aqueous electrolyte. The asymmetric configuration of the masses of both electrodes in the supercapacitor has allowed to cover a higher potential window, resulting in an increase of the energy density of the three devices studied when compared with the symmetric systems, and an improved cycle life.

  2. A First Synthesis and Physical Properties of Asymmetric Anthracenes-Thiophenes Bridged with Ethylene

    International Nuclear Information System (INIS)

    Hwang, Min Ji; Park, Ji Hee; Jeong, Eun Bin

    2012-01-01

    Here we report our recent result of a new semiconductor material, which has an asymmetric structure. The synthesized molecules consist of anthracene and thiophene connected by bridged ethylene and substituted with hexyl or dodecyl groups as pendants. The semiconductors were synthesized using a McMurry coupling reaction between anthracene-2-carbaldehyde and corresponding 5-hexyl(or dodecyl)thiophene-2-carbaldehyde. A first investigation of synthesized asymmetry AVHT (9a) and AVDT (9b) for the physical properties showed that they have high oxidation potential and thermal stability. The devices prepared by using AVHT (9a) and AVDT (9b) showed the mobility of 2.6 Χ 10 -2 cm 2 /Vs and 4.4 Χ 10 -3 cm 2 /Vs, respectively, in solution processed OTFTs

  3. Ion Motion Stability in Asymmetric Surface Electrode Ion Traps

    Science.gov (United States)

    Shaikh, Fayaz; Ozakin, Arkadas

    2010-03-01

    Many recently developed designs of the surface electrode ion traps for quantum information processing have asymmetry built into their geometries. The asymmetry helps rotate the trap axes to angles with respect to electrode surface that facilitate laser cooling of ions but introduces a relative angle between the RF and DC fields and invalidates the classical stability analysis of the symmetric case for which the equations of motion are decoupled. For asymmetric case the classical motion of a single ion is given by a coupled, multi-dimensional version of Mathieu's equation. In this poster we discuss the stability diagram of asymmetric surface traps by performing an approximate multiple scale perturbation analysis of the coupled Mathieu equations, and validate the results with numerical simulations. After obtaining the stability diagram for the linear fields, we simulate the motion of an ion in a given asymmetric surface trap, utilizing a method-of-moments calculation of the electrode fields. We obtain the stability diagram and compare it with the ideal case to find the region of validity. Finally, we compare the results of our stability analysis to experiments conducted on a microfabricated asymmetric surface trap.

  4. Asymmetric information and list-price reductions in the housing market

    NARCIS (Netherlands)

    de Wit, E.; van der Klaauw, B.

    2013-01-01

    In housing markets with asymmetric information list prices may signal unobserved properties of the house or the seller. Asymmetric information is the starting point for many models for the housing market. In this paper, we estimate the causal effect of list-price reductions on the time houses remain

  5. Horner Syndrome

    Science.gov (United States)

    ... of the protective sheath on neurons (myelin) Neck trauma Cyst or cavity in the spinal column (syringomyelia) Second-order neurons This neuron path extends from the spinal column, across the upper part of the chest and into the side of the neck. Causes ...

  6. JET and COMPASS asymmetrical disruptions

    Czech Academy of Sciences Publication Activity Database

    Gerasimov, S.N.; Abreu, P.; Baruzzo, M.; Drozdov, V.; Dvornova, A.; Havlíček, Josef; Hender, T.C.; Hronová-Bilyková, Olena; Kruezi, U.; Li, X.; Markovič, Tomáš; Pánek, Radomír; Rubinacci, G.; Tsalas, M.; Ventre, S.; Villone, F.; Zakharov, L.E.

    2015-01-01

    Roč. 55, č. 11 (2015), s. 113006-113006 ISSN 0029-5515 R&D Projects: GA MŠk(CZ) LM2011021 Institutional support: RVO:61389021 Keywords : tokamak * asymmetrical disruption * JET * COMPASS Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 4.040, year: 2015

  7. Magnetically Modified Asymmetric Supercapacitors, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — This Small Business Innovation Research Phase I project is for the development of an asymmetric supercapacitor that will have improved energy density and cycle life....

  8. Chiral Pyridinium Phosphoramide as a Dual Brønsted Acid Catalyst for Enantioselective Diels-Alder Reaction.

    Science.gov (United States)

    Nishikawa, Yasuhiro; Nakano, Saki; Tahira, Yuu; Terazawa, Kanako; Yamazaki, Ken; Kitamura, Chitoshi; Hara, Osamu

    2016-05-06

    Chiral pyridinium phosphoramide 1·HX was designed to be a new class of chiral Brønsted acid catalyst in which both the pyridinium proton and the adjacent imide-like proton activated by the electron-withdrawing pyridinium moiety could work cooperatively as strong dual proton donors. The potential of 1·HX was shown in the enantioselective Diels-Alder reactions of 1-amino dienes with various dienophiles including N-unsubstituted maleimide, which has yet to be successfully used in an asymmetric Diels-Alder reaction.

  9. Ideal MHD beta-limits of poloidally asymmetric equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Todd, A.M.M.; Miller, A.E.; Grimm, R.C.; Okabayashi, M.; Dalhed, H.E. Jr.

    1981-05-01

    The ideal MHD stability of poloidally asymmetric equilibria, which are typical of a tokamak reactor design with a single-null poloidal divertor is examined. As with symmetric equilibria, stability to non-axisymmetric modes improves with increasing triangularity and ellipticity, and with lower edge safety factor. Pressure profiles optimized with respect to ballooning stability are obtained for an asymmetric shape, resulting in ..beta../sub critical/ approx. = 5.7%. The corresponding value for an equivalent symmetric shape is ..beta../sub critical/ approx. = 6.5%.

  10. Ideal MHD beta-limits of poloidally asymmetric equilibria

    International Nuclear Information System (INIS)

    Todd, A.M.M.; Miller, A.E.; Grimm, R.C.; Okabayashi, M.; Dalhed, H.E. Jr.

    1981-05-01

    The ideal MHD stability of poloidally asymmetric equilibria, which are typical of a tokamak reactor design with a single-null poloidal divertor is examined. As with symmetric equilibria, stability to non-axisymmetric modes improves with increasing triangularity and ellipticity, and with lower edge safety factor. Pressure profiles optimized with respect to ballooning stability are obtained for an asymmetric shape, resulting in β/sub critical/ approx. = 5.7%. The corresponding value for an equivalent symmetric shape is β/sub critical/ approx. = 6.5%

  11. Six transformer based asymmetrical embedded Z-source inverters

    DEFF Research Database (Denmark)

    Wei, Mo; Poh Chiang, Loh; Chi, Jin

    2013-01-01

    Embedded/Asymmetrical embedded Z-source inverters were proposed to maintain smooth input current/voltage across the dc source and within the impedance network, remain the shoot-through feature used to boost up the dc-link voltage without adding bulky filter at input side. This paper introduces a ...... a class of transformer based asymmetrical embedded Z-source inverters which keep the smooth input current and voltage while achieving enhanced voltage boost capability. The presented inverters are verified by laboratory prototypes experimentally....

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

    Science.gov (United States)

    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 α-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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synchronised and complementary coordination mechanisms in an asymmetric joint aiming task

    DEFF Research Database (Denmark)

    Skewes, Joshua Charles; Skewes, Lea; Michael, John

    2015-01-01

    Many forms of social interaction require that behaviour be coordinated in the here and now. Much research has been conducted on how people coordinate their actions in real time to achieve a joint goal, showing that people use both synchronised (i.e. symmetric) and complementary (i.e. asymmetric) ...... in this asymmetric task, as people synchronise better with an irregular, but adaptive partner, than with a completely predictable, but non-responsive metronome. These results show that given asymmetric task constraints, adaptability, rather than predictability facilitates coordination....

  14. Capability of DFIG WTS to ride through recurring asymmetrical grid faults

    DEFF Research Database (Denmark)

    Chen, Wenjie; Blaabjerg, Frede; Chen, Min

    2014-01-01

    The Wind Turbine Systems (WTS) are required to ride through recurring grid faults in some countries. In this paper, the capability of Doubly Fed Induction Generator (DFIG) WTS to ride through recurring asymmetrical grid faults is evaluated and compared with the ride through capability under single...... asymmetrical grid fault. A mathematical model of the DFIG under recurring asymmetrical grid faults is represented. The analysis are verified by simulations on a 1.5MW DFIG model and by experiments on a reduced-scale DFIG test system....

  15. Polymer and Membrane Design for Low Temperature Catalytic Reactions

    KAUST Repository

    Villalobos, Luis Francisco; Xie, Yihui; Nunes, Suzana Pereira; Peinemann, Klaus-Viktor

    2016-01-01

    Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane's ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Polymer and Membrane Design for Low Temperature Catalytic Reactions

    KAUST Repository

    Villalobos, Luis Francisco

    2016-02-29

    Catalytically active asymmetric membranes have been developed with high loadings of palladium nanoparticles located solely in the membrane\\'s ultrathin skin layer. The manufacturing of these membranes requires polymers with functional groups, which can form insoluble complexes with palladium ions. Three polymers have been synthesized for this purpose and a complexation/nonsolvent induced phase separation followed by a palladium reduction step is carried out to prepare such membranes. Parameters to optimize the skin layer thickness and porosity, the palladium loading in this layer, and the palladium nanoparticles size are determined. The catalytic activity of the membranes is verified with the reduction of a nitro-compound and with a liquid phase Suzuki-Miyaura coupling reaction. Very low reaction times are observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Influence of artificial tip perturbation on asymmetric vortices flow over a chined fuselage

    Directory of Open Access Journals (Sweden)

    Shi Wei

    2015-08-01

    Full Text Available An experimental study was conducted with the aim of understanding behavior of asymmetric vortices flow over a chined fuselage. The tests were carried out in a wind tunnel at Reynolds number of 1.87 × 105 under the conditions of high angles of attack and zero angle of sideslip. The results show that leeward vortices flow becomes asymmetric vortices flow when angle of attack increases over 20°. The asymmetric vortices flow is asymmetry of two forebody vortices owing to the increase of angle of attack but not asymmetry of vortex breakdown which appears when angle of attack is above 35°. Asymmetric vortices flow is sensitive to tip perturbation and is non-deterministic due to randomly distributed natural minute geometrical irregularities on the nose tip within machining tolerance. Deterministic asymmetric vortices flow can be obtained by attaching artificial tip perturbation which can trigger asymmetric vortices flow and decide asymmetric vortices flow pattern. Triggered by artificial tip perturbation, the vortex on the same side with perturbation is in a higher position, and the other vortex on the opposite side is in a lower position. Vortex suction on the lower vortex side is larger, which corresponds to a side force pointing to the lower vortex side.

  18. Asymmetrical intrapleural pressure distribution: a cause for scoliosis? A computational analysis.

    Science.gov (United States)

    Schlager, Benedikt; Niemeyer, Frank; Galbusera, Fabio; Wilke, Hans-Joachim

    2018-04-13

    The mechanical link between the pleural physiology and the development of scoliosis is still unresolved. The intrapleural pressure (IPP) which is distributed across the inner chest wall has yet been widely neglected in etiology debates. With this study, we attempted to investigate the mechanical influence of the IPP distribution on the shape of the spinal curvature. A finite element model of pleura, chest and spine was created based on CT data of a patient with no visual deformities. Different IPP distributions at a static end of expiration condition were investigated, such as the influence of an asymmetry in the IPP distribution between the left and right hemithorax. The results were then compared to clinical data. The application of the IPP resulted in a compressive force of 22.3 N and a flexion moment of 2.8 N m at S1. An asymmetrical pressure between the left and right hemithorax resulted in lateral deviation of the spine towards the side of the reduced negative pressure. In particular, the pressure within the dorsal section of the rib cage had a strong influence on the vertebral rotation, while the pressure in medial and ventral region affected the lateral displacement. An asymmetrical IPP caused spinal deformation patterns which were comparable to deformation patterns seen in scoliotic spines. The calculated reaction forces suggest that the IPP contributes in counterbalancing the weight of the intrathoracic organs. The study confirms the potential relevance of the IPP for spinal biomechanics and pathologies, such as adolescent idiopathic scoliosis.

  19. Autorefraction versus subjective refraction in a radially asymmetric multifocal intraocular lens

    NARCIS (Netherlands)

    Linden, J.W.M. van der; Vrijman, V.; El-Saady, R.; Meulen, I.J. van der; Mourits, M.P.; Lapid-Gortzak, R.

    2014-01-01

    PURPOSE: To evaluate whether the automated refraction (AR) correlates with subjective manifest (MR) refraction in eyes implanted with radially asymmetric multifocal intraocular lens (IOLs). METHODS: This retrospective study evaluated 52 eyes (52 patients) implanted with a radially asymmetric

  20. Mass and charge distributions in Fe-induced reactions

    International Nuclear Information System (INIS)

    Madani, H.; Mignerey, A.C.; Marchetti, A.A.; Weston-Dawkes, A.P.; Kehoe, W.L.; Obenshain, F.

    1995-01-01

    The charge and mass of the projectile-like fragments produced in the 12-MeV/nucleon 56 Fe + 165 Ho reaction were measured at a laboratory scattering angle of 16 degrees. The mass and charge distributions of the projectile-like fragments were generated as a function of total kinetic energy loss (TKEL), and characterized by their neutron and proton centroids and variances, and correlation factors. A weak drift of the system towards mass asymmetry, opposite to the direction which minimizes the potential energy of the composite system, was observed. The increase in the variances with energy loss is consistent with a nucleon exchange mechanism as a means for energy dissipation. Predictions of two nucleon exchange models, Randrup's and, Tassan-Got's models, are compared to the experimental results of the 672-MeV 56 Fe + 165 Ho reaction and to other Fe-induced reactions. The proton and neutron centroids were found to be generally better reproduced by Tassan-Got's model than by Randrup's model. The variances and correlation factor are well reproduced for asymmetric systems by both models

  1. Electron Jet of Asymmetric Reconnection

    Science.gov (United States)

    Khotyaintsev, Yu. V.; Graham, D. B.; Norgren, C.; Eriksson, E.; Li, W.; Johlander, A.; Vaivads, A.; Andre, M.; Pritchett, P. L.; Retino, A.; hide

    2016-01-01

    We present Magnetospheric Multiscale observations of an electron-scale current sheet and electron outflow jet for asymmetric reconnection with guide field at the subsolar magnetopause. The electron jet observed within the reconnection region has an electron Mach number of 0.35 and is associated with electron agyrotropy. The jet is unstable to an electrostatic instability which generates intense waves with E(sub parallel lines) amplitudes reaching up to 300 mV/m and potentials up to 20% of the electron thermal energy. We see evidence of interaction between the waves and the electron beam, leading to quick thermalization of the beam and stabilization of the instability. The wave phase speed is comparable to the ion thermal speed, suggesting that the instability is of Buneman type, and therefore introduces electron-ion drag and leads to braking of the electron flow. Our observations demonstrate that electrostatic turbulence plays an important role in the electron-scale physics of asymmetric reconnection.

  2. Field factors for asymmetric collimators

    International Nuclear Information System (INIS)

    Turner, J.R.; Butler, A.P.H.

    1996-01-01

    In recent years manufacturers have been supplying linear accelerators with either a single pair or a dual pair of collimators. The use of a model to relate off-axis field factors to on-axis field factors obviates the need for repeat measurements whenever the asymmetric collimators are employed. We have investigated the variation of collimator scatter Sc, with distance of the central ray x from the central axis for a variety of non square field sizes. Collimator scatter was measured by in-air measurements with a build-up cap. The Primaty-Off-Centre-Ratio (POCR) was measured in-air by scanning orthogonally across the beam with an ionization chamber. The result of the investigation is the useful prediction of off-axis field factors for a range of rectangular asymmetric fields using the simple product of the on-axis field factor and the POCR in air. The effect of asymmetry on the quality of the beam and hence the percent depth dose will be discussed. (author)

  3. The effects of asymmetric directional microphone fittings on acceptance of background noise.

    Science.gov (United States)

    Kim, Jong S; Bryan, Melinda Freyaldenhoven

    2011-05-01

    The effects of asymmetric directional microphone fittings (i.e., an omnidirectional microphone on one ear and a directional microphone on the other) on speech understanding in noise and acceptance of background noise were investigated in 15 full-time hearing aid users. Subjects were fitted binaurally with four directional microphone conditions (i.e., binaural omnidirectional, right asymmetric directional, left asymmetric directional and binaural directional microphones) using Siemens Intuis Directional behind-the-ear hearing aids. Speech understanding in noise was assessed using the Hearing in Noise Test, and acceptance of background noise was assessed using the Acceptable Noise Level procedure. Speech was presented from 0° while noise was presented from 180° azimuth. The results revealed that speech understanding in noise improved when using asymmetric directional microphones compared to binaural omnidirectional microphone fittings and was not significantly hindered compared to binaural directional microphone fittings. The results also revealed that listeners accepted more background noise when fitted with asymmetric directional microphones as compared to binaural omnidirectional microphones. Lastly, the results revealed that the acceptance of noise was further increased for the binaural directional microphones when compared to the asymmetric directional microphones, maximizing listeners' willingness to accept background noise in the presence of noise. Clinical implications will be discussed.

  4. Hierarchical VOOH hollow spheres for symmetrical and asymmetrical supercapacitor devices

    Science.gov (United States)

    Jing, Xuyang; Wang, Cong; Feng, Wenjing; Xing, Na; Jiang, Hanmei; Lu, Xiangyu; Zhang, Yifu; Meng, Changgong

    2018-01-01

    Hierarchical VOOH hollow spheres with low crystallinity composed of nanoparticles were prepared by a facile and template-free method, which involved a precipitation of precursor microspheres in aqueous solution at room temperature and subsequent hydrothermal reaction. Quasi-solid-state symmetric and asymmetric supercapacitor (SSC and ASC) devices were fabricated using hierarchical VOOH hollow spheres as the electrodes, and the electrochemical properties of the VOOH//VOOH SSC device and the VOOH//AC ASC device were studied by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). Results demonstrated that the electrochemical performance of the VOOH//AC ASC device was better than that of the VOOH//VOOH SSC device. After 3000 cycles, the specific capacitance of the VOOH//AC ASC device retains 83% of the initial capacitance, while the VOOH//VOOH SSC device retains only 7.7%. Findings in this work proved that hierarchical VOOH hollow spheres could be a promising candidate as an ideal electrode material for supercapacitor devices.

  5. Efficient and Selective Syntheses of (all-E)- and (6E,10Z)-2′-O-Methylmyxalamides D via Pd-Catalyzed Alkenylation—Carbonyl Olefination Synergy

    Science.gov (United States)

    Wang, Guangwei; Huang, Zhihong; Negishi, Ei-ichi

    2008-01-01

    Highly efficient and selective syntheses of both (all-E) and (6E,10Z)-isomers of 2′-O-methylmyxalamide D (2 and 3), in which the crucial conjugated pentaene moieties were assembled in ≥98% stereoselectivity through the use of two Pd-catalyzed alkenylation reactions, the Horner—Wadsworth—Emmons (HWE) olefination, and either the Corey—Schlessinger—Mills modified (CSM-modified) Peterson olefination for 2 or the Still—Gennari olefination for 3, are reported. Either 2 or 3 was prepared in 16% yield in seven steps from propargyl alcohol. PMID:18593171

  6. Beam-beam issues in asymmetric colliders

    International Nuclear Information System (INIS)

    Furman, M.A.

    1992-07-01

    We discuss generic beam-beam issues for proposed asymmetric e + - e - colliders. We illustrate the issues by choosing, as examples, the proposals by Cornell University (CESR-B), KEK, and SLAC/LBL/LLNL (PEP-II)

  7. Autorefraction versus subjective refraction in a radially asymmetric multifocal intraocular lens

    NARCIS (Netherlands)

    van der Linden, Jan Willem; Vrijman, Violette; Al-Saady, Rana; El-Saady, Rana; van der Meulen, Ivanka J.; Mourits, Maarten P.; Lapid-Gortzak, Ruth

    2014-01-01

    To evaluate whether the automated refraction (AR) correlates with subjective manifest (MR) refraction in eyes implanted with radially asymmetric multifocal intraocular lens (IOLs). This retrospective study evaluated 52 eyes (52 patients) implanted with a radially asymmetric multifocal IOL (LS-312

  8. The asymmetric rotator model applied to odd-mass iridium isotopes

    International Nuclear Information System (INIS)

    Piepenbring, R.

    1980-04-01

    The method of inversion of the eigenvalue problem previously developed for nuclei with axial symmetry is extended to asymmetric equilibrium shapes. This new approach of the asymmetric rotator model is applied to the odd-mass iridium isotopes. A satisfactory and coherent description of the observed energy spectra is obtained, especially for the lighter isotopes

  9. Neutron optical potentials in unstable nuclei and the equation of state of asymmetric nuclear matter

    International Nuclear Information System (INIS)

    Oyamatsu, K.; Iida, K.

    2003-01-01

    Neutron single particle potential is one of the basic macroscopic properties to describe structure and reactions of nuclei in nuclear reactors and in the universe. However, the potential is quite uncertain for unstable nuclei primarily because the equation of state (EOS) of asymmetric nuclear matter is not known well. The present authors studied systematically the empirical EOS of asymmetric nuclear matter using a macroscopic nuclear model; about two hundred EOS's having empirically allowed values of L (symmetry energy density derivative coefficient) and K 0 (incompressibility) were obtained from the fittings to masses and radii of stable nuclei. It was suggested that the L value could be determined from global (Z, A) dependence of nuclear radii. In the present study, the single particle potential is examined assuming kinetic energies of non-interacting Fermi gases. The potential in a nucleus can be calculated easily, once the density distribution is solved using the effective nuclear interaction (EOS). Neutron and proton single particle potentials are calculated systematically for 80 Ni using the two hundred EOS's. It is found that the neutron-proton potential difference has clear and appreciable L dependence, while the potential for each species does not show such simple dependence on L. (author)

  10. Asymmetric Facial Bone Fragmentation Mirrors Asymmetric Distribution of Cranial Neuromasts in Blind Mexican Cavefish

    Directory of Open Access Journals (Sweden)

    Joshua B. Gross

    2016-10-01

    Full Text Available Craniofacial asymmetry is a convergent trait widely distributed across animals that colonize the extreme cave environment. Although craniofacial asymmetry can be discerned easily, other complex phenotypes (such as sensory organ position and numerical variation are challenging to score and compare. Certain bones of the craniofacial complex demonstrate substantial asymmetry, and co-localize to regions harboring dramatically expanded numbers of mechanosensory neuromasts. To determine if a relationship exists between this expansion and bone fragmentation in cavefish, we developed a quantitative measure of positional symmetry across the left-right axis. We found that three different cave-dwelling populations were significantly more asymmetric compared to surface-dwelling fish. Moreover, cave populations did not differ in the degree of neuromast asymmetry. This work establishes a method for quantifying symmetry of a complex phenotype, and demonstrates that facial bone fragmentation mirrors the asymmetric distribution of neuromasts in different cavefish populations. Further developmental studies will provide a clearer picture of the developmental and cellular changes that accompany this extreme phenotype, and help illuminate the genetic basis for facial asymmetry in vertebrates.

  11. Impact of asymmetric lamp positioning on the performance of a closed-conduit UV reactor

    Directory of Open Access Journals (Sweden)

    Tipu Sultan

    2017-06-01

    Full Text Available Computational fluid dynamics (CFD analyses for the performance improvement of a closed-conduit ultraviolet (UV reactor were performed by changing the lamp positions from symmetric to asymmetric. The asymmetric lamp positioning can be useful for UV reactor design and optimization. This goal was achieved by incorporating the two performance factors, namely reduction equivalent dose (RED and system dose performance. Four cases were carried out for asymmetric lamp positioning within the UV reactor chamber and each case consisted of four UV lamps that were simulated once symmetrically and four times asymmetrically. The results of the four asymmetric cases were compared with the symmetric one. Moreover, these results were evaluated by using CFD simulations of a closed-conduit UV reactor. The fluence rate model, UVCalc3D was employed to validate the simulations results. The simulation results provide detailed information about the dose distribution, pathogen track modeling and RED. The RED value was increased by approximately 15% by using UVCalc3D fluence rate model. Additionally, the asymmetric lamp positioning of the UV lamps had more than 50% of the pathogens received a better and a higher UV dose than in the symmetric case. Consequently, the system dose performance was improved by asymmetric lamp positioning. It was concluded that the performance parameters (higher RED and system dose performance were improved by using asymmetric lamp positioning.

  12. Electron Raman scattering in asymmetrical multiple quantum wells

    International Nuclear Information System (INIS)

    Betancourt-Riera, R; Rosas, R; Marin-Enriquez, I; Riera, R; Marin, J L

    2005-01-01

    Optical properties of asymmetrical multiple quantum wells for the construction of quantum cascade lasers are calculated, and expressions for the electronic states of asymmetrical multiple quantum wells are presented. The gain and differential cross-section for an electron Raman scattering process are obtained. Also, the emission spectra for several scattering configurations are discussed, and the corresponding selection rules for the processes involved are studied; an interpretation of the singularities found in the spectra is given. The electron Raman scattering studied here can be used to provide direct information about the efficiency of the lasers

  13. Preview-based Asymmetric Load Reduction of Wind Turbines

    DEFF Research Database (Denmark)

    Madsen, Mathias; Filsø, Jakob; Soltani, Mohsen

    2012-01-01

    Controller (MPC) developed is based on a model with individual blade pitching to utilize the LIDAR measurements. The MPC must also maintain a given power reference while satisfying a set of actuator constraints. The designed controller was tested on a 5 MW wind turbine in the FAST simulator and compared......Fatigue loads on wind turbines caused by an asymmetric wind field become an increasing concern when the scale of wind turbines increases. This paper presents a model based predictive approach to reduce asymmetric loads by using Light Detection And Ranging (LIDAR) measurements. The Model Predictive...

  14. Prospects of asymmetrically H-terminated zigzag germanene nanoribbons for spintronic application

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Varun, E-mail: varun@iiitm.ac.in [Nanomaterials Research Group, ABV-Indian Institute of Information Technology and Management (IIITM), Gwalior 474015 (India); Srivastava, Pankaj [Nanomaterials Research Group, ABV-Indian Institute of Information Technology and Management (IIITM), Gwalior 474015 (India); Jaiswal, Neeraj K. [Discipline of Physics, Indian Institute of Information Technology, Design & Manufacturing, Jabalpur, Dumna Airport Road, Jabalpur 482005 (India)

    2017-02-28

    Highlights: • Asymmetric hydrogen termination of Zigzag Germanene Nanoribbons (ZGeNR) is presented with their plausible spintronic device application. • It is revealed that asymmetric terminations are energetically more favourable compared to symmetric terminations. • The magnetic moment analysis depicts that asymmetric ZGeNR have a magnetic ground state with a preferred ferromagnetic (FM) coupling. • Presented doped asymmetric ZGeNR exhibits a half-metallic character which makes them qualify for spin-filtering device. - Abstract: First-principles investigations have been performed to explore the spin based electronic and transport properties of asymmetrically H-terminated zigzag germanene nanoribbons (2H−H ZGeNR). Investigations reveal a significant formation energy difference (ΔE{sub F} = E{sub F(2H-H)} − E{sub F(H-H)} ∼ −0.49 eV), highlighting more energetic stability for asymmetric edge termination compared to symmetric edge termination, irrespective of the ribbon width. Further, magnetic moment analysis and total energy calculations were performed to unveil that these structures have a magnetic ground state with preferred ferromagnetic (FM) coupling. The calculated E-k structures project a unique bipolar semiconducting behaviour for 2H−H ZGeNR which is contrast to H-terminated ZGeNR. Half-metallic transformation has also been revealed via suitable p-type or n-type doping for these structures. Finally, transport calculations were performed to highlight the selective contributions of spin-down (spin-up) electrons in the I–V characteristics of the doped 2H−H ZGeNR, suggesting their vitality for spintronic device applications.

  15. Asymmetric total synthesis of 6-Tuliposide B and its biological activities against tulip pathogenic fungi.

    Science.gov (United States)

    Shigetomi, Kengo; Omoto, Shoko; Kato, Yasuo; Ubukata, Makoto

    2011-01-01

    The structure-activity relationship was investigated to evaluate the antifungal activities of tuliposides and tulipalins against tulip pathogenic fungi. 6-Tuliposide B was effectively synthesized via the asymmetric Baylis-Hillman reaction. Tuliposides and tulipalins showed antifungal activities against most of the strains tested at high concentrations (2.5 mM), while Botrytis tulipae was resistant to tuliposides. Tulipalin formation was involved in the antifungal activity, tulipalin A showed higher inhibitory activity than 6-tuliposide B and tulipalin B. Both the tuliposides and tulipalins showed pigment-inducing activity against Gibberella zeae and inhibitory activity against Fusarium oxysporum f. sp tulipae. These activities were induced at a much lower concentration (0.05 mM) than the antifungal MIC values.

  16. The Respiratory Impedance in an Asymmetric Model of the Lung Structure

    Directory of Open Access Journals (Sweden)

    Robin De Keyser

    2011-01-01

    Full Text Available This paper presents a model of the respiratory tree as a recurrent, but asymmetric, structure. The intrinsic properties posed by such a system lead to a multi-fractal structure, i.e. a non-integer order model of the total impedance. The fractional order behavior of the asymmetric tree simulated as a dynamic system is assessed by means of Bode plots, on a wide range of frequencies. The results indicate than in a specific frequency range, both the symmetric
    and asymmetric representation of the respiratory tree lead to similar values in the impedance.

  17. Test of distorted wave kinematic coupling approximation calculations for knockout reactions

    International Nuclear Information System (INIS)

    Jain, A.K.

    1990-01-01

    A test has been devised to check the validity of conventional distorted-wave impulse approximation (DWIA) treatment of knockout reactions. The conventional DWIA formalism separates the three-body final state Schroedinger equation for a knockout reaction into two two-body Schroedinger equations by assuming an asymptotic constant value for the three-body coupling term commonly known as the kinematic coupling approximation (KCA). In the test case, which consists of an extreme asymmetric situation where one of the distorting optical potentials is assumed to vanish, the three-body final state Schroedinger equation can be solved exactly as a product of two two-body solutions using one particular set of relative coordinates. Large influence of the three-body coupling term is seen in the comparison of the exact and KCA results for (α,2α) and (p,pα) knockout reactions when the distorting optical potentials are weakly absorbing

  18. Between Confessionalism and Liberal Conservatism : The Christian Democratic Parties of Belgium and the Netherlands

    NARCIS (Netherlands)

    Lucardie, Anthonie; Ten Napel, Hans_Martien; Hanley, David

    1994-01-01

    According to Horner (1981), the Christian Democratic parties of the Low Countries are still confessional parties (Konjessionsparteien) , whereas their sister parties in Germany and Italy are evolving towards liberal conservative catch-all parties (Volksparteien). In this chapter Horner's thesis will

  19. Highly enantioselective access to cannabinoid-type tricyles by organocatalytic Diels–Alder reactions

    Directory of Open Access Journals (Sweden)

    Stefan Bräse

    2012-08-01

    Full Text Available After prosperous domino reactions towards benzopyrans, the products were used as the starting material in Lewis acid catalyzed and organocatalytic Diels–Alder reactions to build up a tricyclic system. Herein, an asymmetric induction up to 96% enantiomeric excess was obtained by the use of imidazolidinone catalysts. This approach can be utilized to construct the tricyclic system in numerous natural products, in particular the scaffold of tetrahydrocannabinol (THC being the most representative one. Compared with other published methods, condensation with a preexisting cyclohexane moiety in the precursor is needed to gain the heterogenic tricycle systems, whereas we present a novel strategy towards cannabinoid derivatives based on a flexible modular synthesis.

  20. Ultrasound-Accelerated Synthesis of Asymmetrical Thiosulfonate S-Esters by Base-Promoted Reaction of Sulfonyl Chlorides with Thiols

    DEFF Research Database (Denmark)

    Pham, Hien Thi; Nguyen, Ngoc-Lan Thi; Duus, Fritz

    2015-01-01

    Amberlyst A-26, Mg-Al hydrotalcite, potassium fluoride absorbed on alumina, triethylamine and pyridine have been tested as base catalysts and reagents for the reaction of sulfonyl chlorides with thiols to prepare thiosulfonate S-esters. The reactions were performed under solvent-free conditions...

  1. Process for fabricating PBI hollow fiber asymmetric membranes for gas separation and liquid separation

    Science.gov (United States)

    Jayaweera, Indira; Krishnan, Gopala N.; Sanjurjo, Angel; Jayaweera, Palitha; Bhamidi, Srinivas

    2016-04-26

    The invention provides methods for preparing an asymmetric hollow fiber, the asymmetric hollow fibers prepared by such methods, and uses of the asymmetric hollow fibers. One method involves passing a polymeric solution through an outer annular orifice of a tube-in-orifice spinneret, passing a bore fluid though an inner tube of the spinneret, dropping the polymeric solution and bore fluid through an atmosphere over a dropping distance, and quenching the polymeric solution and bore fluid in a bath to form an asymmetric hollow fiber.

  2. Electrochemical capacitance of NiO/Ru{sub 0.35}V{sub 0.65}O{sub 2} asymmetric electrochemical capacitor

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Chang-Zhou; Gao, Bo; Zhang, Xiao-Gang [College of Material Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016 (China)

    2007-11-08

    A designed asymmetric hybrid electrochemical capacitor was presented where NiO and Ru{sub 0.35}V{sub 0.65}O{sub 2} as the positive and negative electrode, respectively, both stored charge through reversible faradic pseudocapacitive reactions of the anions (OH{sup -}) with electroactive materials. And the two electrodes had been individually tested in 1 M KOH aqueous electrolyte to define the adequate balance of the active materials in the hybrid system as well as the working voltage of the capacitor based on them. The electrochemical tests demonstrated that the maximum specific capacitance and energy density of the asymmetric hybrid electrochemical capacitor were 102.6 F g{sup -1} and 41.2 Wh kg{sup -1}, respectively, delivered at a current density of 7.5 A cm{sup -2}. And the specific energy density decreased to 23.0 Wh kg{sup -1} when the specific power density increased up to 1416.7 W kg{sup -1}. The hybrid electrochemical capacitor also exhibited a good electrochemical stability with 83.5% of the initial capacitance over consecutive 1500 cycle numbers. (author)

  3. The influence of the entrance channel mass asymmetry on the reaction mechanism

    International Nuclear Information System (INIS)

    Agarwal, S.; Galin, J.; Gatty, B.; Guerreau, D.; Lefort, M.; Tarrago, X.; Babinet, R.; Girard, J.

    1980-01-01

    We have tried to investigate the influence of the entrance channel mass asymmetry on the reaction mechanisms associated with heavy ion collisions. Two systems, one very much asymmetric (O + Mo) and the other one almost symmetric (Cr + Fe), were studied in detail by measuring evaporation residues, deep inelastic collision products and fission fragments. An important fraction of the fragments observed in the Cr + Fe system exhibits all the characteristics of fission fragments. The analysis of these data seems to indicate that these fission like products are most likely emitted by a long lived composite system having not reached full statistical equilibrium for all the degrees of freedom. As a consequence, the fusion cross section for this symmetric system is too low as compared to predictions based on a critical distance approach for fusion, whereas the asymmetric system (O + Mo) is well understood in terms of the same model. (orig.)

  4. Bianisotropic metamaterials based on twisted asymmetric crosses

    International Nuclear Information System (INIS)

    Reyes-Avendaño, J A; Sampedro, M P; Juárez-Ruiz, E; Pérez-Rodríguez, F

    2014-01-01

    The effective bianisotropic response of 3D periodic metal-dielectric structures, composed of crosses with asymmetrically-cut wires, is investigated within a general homogenization theory using the Fourier formalism and the form-factor division approach. It is found that the frequency dependence of the effective permittivity for a system of periodically-repeated layers of metal crosses exhibits two strong resonances, whose separation is due to the cross asymmetry. Besides, bianisotropic metamaterials, having a base of four twisted asymmetric crosses, are proposed. The designed metamaterials possess negative refractive index at frequencies determined by the cross asymmetry, the gap between the arms of adjacent crosses lying on the same plane, and the type of Bravais lattice. (papers)

  5. Asymmetric Distribution of GFAP in Glioma Multipotent Cells

    Science.gov (United States)

    Guichet, Pierre-Olivier; Guelfi, Sophie; Ripoll, Chantal; Teigell, Marisa; Sabourin, Jean-Charles; Bauchet, Luc; Rigau, Valérie; Rothhut, Bernard; Hugnot, Jean-Philippe

    2016-01-01

    Asymmetric division (AD) is a fundamental mechanism whereby unequal inheritance of various cellular compounds during mitosis generates unequal fate in the two daughter cells. Unequal repartitions of transcription factors, receptors as well as mRNA have been abundantly described in AD. In contrast, the involvement of intermediate filaments in this process is still largely unknown. AD occurs in stem cells during development but was also recently observed in cancer stem cells. Here, we demonstrate the asymmetric distribution of the main astrocytic intermediate filament, namely the glial fibrillary acid protein (GFAP), in mitotic glioma multipotent cells isolated from glioblastoma (GBM), the most frequent type of brain tumor. Unequal mitotic repartition of GFAP was also observed in mice non-tumoral neural stem cells indicating that this process occurs across species and is not restricted to cancerous cells. Immunofluorescence and videomicroscopy were used to capture these rare and transient events. Considering the role of intermediate filaments in cytoplasm organization and cell signaling, we propose that asymmetric distribution of GFAP could possibly participate in the regulation of normal and cancerous neural stem cell fate. PMID:26953813

  6. Asymmetric Distribution of GFAP in Glioma Multipotent Cells.

    Directory of Open Access Journals (Sweden)

    Pierre-Olivier Guichet

    Full Text Available Asymmetric division (AD is a fundamental mechanism whereby unequal inheritance of various cellular compounds during mitosis generates unequal fate in the two daughter cells. Unequal repartitions of transcription factors, receptors as well as mRNA have been abundantly described in AD. In contrast, the involvement of intermediate filaments in this process is still largely unknown. AD occurs in stem cells during development but was also recently observed in cancer stem cells. Here, we demonstrate the asymmetric distribution of the main astrocytic intermediate filament, namely the glial fibrillary acid protein (GFAP, in mitotic glioma multipotent cells isolated from glioblastoma (GBM, the most frequent type of brain tumor. Unequal mitotic repartition of GFAP was also observed in mice non-tumoral neural stem cells indicating that this process occurs across species and is not restricted to cancerous cells. Immunofluorescence and videomicroscopy were used to capture these rare and transient events. Considering the role of intermediate filaments in cytoplasm organization and cell signaling, we propose that asymmetric distribution of GFAP could possibly participate in the regulation of normal and cancerous neural stem cell fate.

  7. Origin of Asymmetric Charge Partitioning in the Dissociation of Gas-Phase Protein Homodimers

    OpenAIRE

    Jurchen, John C.; Williams, Evan R.

    2003-01-01

    The origin of asymmetric charge and mass partitioning observed for gas-phase dissociation of multiply charged macromolecular complexes has been hotly debated. These experiments hold the potential to provide detailed information about the interactions between the macromolecules within the complex. Here, this unusual phenomenon of asymmetric charge partitioning is investigated for several protein homodimers. Asymmetric charge partitioning in these ions depends on a number of factors, including ...

  8. Asymmetric cell division of stem cells in the lung and other systems

    Directory of Open Access Journals (Sweden)

    Mohamed eBerika

    2014-07-01

    Full Text Available New insights have been added to identification, behavior and cellular properties of embryonic and tissue-specific stem cells over the last few years. The modes of stem cell division, asymmetric versus symmetric, are tightly regulated during development and regeneration. The proper choice of a stem cell to divide asymmetrically or symmetrically has great consequences for development and disease because inappropriate asymmetric division disrupts organ morphogenesis, whereas uncontrolled symmetric division induces tumorigenesis. Therefore, understanding the behavior of lung stem cells could identify innovative solutions for restoring normal morphogenesis and/or regeneration of different organs. In this concise review, we describe recent studies in our laboratory about the mode of division of lung epithelial stem cells. We also compare asymmetric cell division in the lung stem cells with other tissues in different organisms.

  9. Catalytic asymmetric dihydroxylation of olefins with reusable OsO(4)(2-) on ion-exchangers: the scope and reactivity using various cooxidants.

    Science.gov (United States)

    Choudary, Boyapati M; Chowdari, Naidu S; Jyothi, Karangula; Kantam, Mannepalli L

    2002-05-15

    Exchanger-OsO(4) catalysts are prepared by an ion-exchange technique using layered double hydroxides and quaternary ammonium salts covalently bound to resin and silica as ion-exchangers. The ion-exchangers with different characteristics and opposite ion selectivities are specially chosen to produce the best heterogeneous catalyst that can operate using the various cooxidants in the asymmetric dihydroxylation reaction. LDH-OsO(4) catalysts composed of different compositions are evaluated for the asymmetric dihydroxylation of trans-stilbene. Resin-OsO(4) and SiO(2)-OsO(4) designed to overcome the problems associated with LDH-OsO(4) indeed show consistent activity and enantioselectivity in asymmetric dihydroxylation of olefins using K(3)Fe(CN)(6) and molecular oxygen as cooxidants. Compared to the Kobayashi heterogeneous systems, resin-OsO(4) is a very efficient catalyst for the dihydroxylation of a wide variety of aromatic, aliphatic, acyclic, cyclic, mono-, di-, and trisubstituted olefins to afford chiral vicinal diols with high yields and enantioselectivities irrespective of the cooxidant used. Resin-OsO(4) is recovered quantitatively by a simple filtration and reused for a number of cycles with consistent activity. The high binding ability of the heterogeneous osmium catalyst enables the use of an equimolar ratio of ligand to osmium to give excellent enantioselectives in asymmetric dihydroxylation in contrast to the homogeneous osmium system in which excess molar quantities of the expensive chiral ligand to osmium are invariably used. The complexation of the chiral ligand (DHQD)(2)PHAL, having very large dimension, a prerequisite to obtain higher ee, is possible only with the OsO(4)(2-) located on the surface of the supports.

  10. Asymmetric Aminalization via Cation-Binding Catalysis

    DEFF Research Database (Denmark)

    Park, Sang Yeon; Liu, Yidong; Oh, Joong Suk

    2018-01-01

    Asymmetric cation-binding catalysis, in principle, can generate "chiral" anionic nucleophiles, where the counter cations are coordinated within chiral environments. Nitrogen-nucleophiles are intrinsically basic, therefore, its use as nucleophiles is often challenging and limiting the scope of the...

  11. Uniform versus asymmetric shading mediates crown recession in conifers.

    Directory of Open Access Journals (Sweden)

    Amanda L Schoonmaker

    Full Text Available In this study we explore the impact of asymmetrical vs. uniform crown shading on the mortality and growth of upper and lower branches within tree crowns, for two conifer species: shade intolerant lodgepole pine (Pinus contorta and shade tolerant white spruce (Picea glauca. We also explore xylem hydraulics, foliar nutrition, and carbohydrate status as drivers for growth and expansion of the lower and upper branches in various types of shading. This study was conducted over a two-year period across 10 regenerating forest sites dominated by lodgepole pine and white spruce, in the lower foothills of Alberta, Canada. Trees were assigned to one of four shading treatments: (1, complete uniform shading of the entire tree, (2 light asymmetric shading where the lower 1/4-1/3 of the tree crown was shaded, (3 heavy asymmetric shading as in (2 except with greater light reduction and (4 control in which no artificial shading occurred and most of the entire crown was exposed to full light. Asymmetrical shading of only the lower crown had a larger negative impact on the bud expansion and growth than did uniform shading, and the effect was stronger in pine relative to spruce. In addition, lower branches in pine also had lower carbon reserves, and reduced xylem-area specific conductivity compared to spruce. For both species, but particularly the pine, the needles of lower branches tended to store less C than upper branches in the asymmetric shade, which could suggest a movement of reserves away from the lower branches. The implications of these findings correspond with the inherent shade tolerance and self-pruning behavior of these conifers and supports a carbon based mechanism for branch mortality--mediated by an asymmetry in light exposure of the crown.

  12. Readily Available Chiral Benzimidazoles-Derived Guanidines as Organocatalysts in the Asymmetric α-Amination of 1,3-Dicarbonyl Compounds.

    Science.gov (United States)

    Benavent, Llorenç; Puccetti, Francesco; Baeza, Alejandro; Gómez-Martínez, Melania

    2017-08-11

    The synthesis and the evaluation as organocatalysts of new chiral guanidines derived from benzimidazoles in the enantioselective α-amination of 1,3-dicarbonyl compounds using di- t -butylazodicarboxylate as aminating agent is herein disclosed. The catalysts are readily synthesized through the reaction of 2-chlorobezimidazole and a chiral amine in moderate-to-good yields. Among all of them, those derived from ( R )-1-phenylethan-1-amine ( 1 ) and ( S )-1-(2-naphthyl)ethan-1-amine ( 3 ) turned out to be the most efficient for such asymmetric transformation, rendering good-to-high yields and moderate-to-good enantioselectivities for the amination products.

  13. Diradical character dependences of the first and second hyperpolarizabilities of asymmetric open-shell singlet systems.

    Science.gov (United States)

    Nakano, Masayoshi; Champagne, Benoît

    2013-06-28

    The static first and second hyperpolarizabilities (referred to as β and γ, respectively) of asymmetric open-shell singlet systems have been investigated using the asymmetric two-site diradical model within the valence configuration interaction level of theory in order to reveal the effect of the asymmetric electron distribution on the diradical character and subsequently on β and γ. It is found that the increase of the asymmetric electron distribution causes remarkable changes in the amplitude and the sign of β and γ, and that their variations are intensified with the increase of the diradical character. These results demonstrate that the asymmetric open-shell singlet systems with intermediate diradical characters can exhibit further enhancements of β and γ as compared to conventional asymmetric closed-shell systems and also to symmetric open-shell singlet systems with intermediate diradical characters.

  14. The Chip-Scale Atomic Clock - Prototype Evaluation

    Science.gov (United States)

    2007-11-01

    39th Annual Precise Time and Time Interval (PTTI) Meeting THE CHIP-SCALE ATOMIC CLOCK – PROTOTYPE EVALUATION R. Lutwak *, A. Rashed...been supported by the Defense Advanced Research Projects Agency, Contract # NBCHC020050. REFERENCES [1] R. Lutwak , D. Emmons, W. Riley, and...D.C.), pp. 539-550. [2] R. Lutwak , D. Emmons, T. English, W. Riley, A. Duwel, M. Varghese, D. K. Serkland, and G. M. Peake, 2004, “The Chip-Scale

  15. LG tools for asymmetric wargaming

    Science.gov (United States)

    Stilman, Boris; Yakhnis, Alex; Yakhnis, Vladimir

    2002-07-01

    Asymmetric operations represent conflict where one of the sides would apply military power to influence the political and civil environment, to facilitate diplomacy, and to interrupt specified illegal activities. This is a special type of conflict where the participants do not initiate full-scale war. Instead, the sides may be engaged in a limited open conflict or one or several sides may covertly engage another side using unconventional or less conventional methods of engagement. They may include peace operations, combating terrorism, counterdrug operations, arms control, support of insurgencies or counterinsurgencies, show of force. An asymmetric conflict can be represented as several concurrent interlinked games of various kinds: military, transportation, economic, political, etc. Thus, various actions of peace violators, terrorists, drug traffickers, etc., can be expressed via moves in different interlinked games. LG tools allow us to fully capture the specificity of asymmetric conflicts employing the major LG concept of hypergame. Hypergame allows modeling concurrent interlinked processes taking place in geographically remote locations at different levels of resolution and time scale. For example, it allows us to model an antiterrorist operation taking place simultaneously in a number of countries around the globe and involving wide range of entities from individuals to combat units to governments. Additionally, LG allows us to model all sides of the conflict at their level of sophistication. Intelligent stakeholders are represented by means of LG generated intelligent strategies. TO generate those strategies, in addition to its own mathematical intelligence, the LG algorithm may incorporate the intelligence of the top-level experts in the respective problem domains. LG models the individual differences between intelligent stakeholders. The LG tools make it possible to incorporate most of the known traits of a stakeholder, i.e., real personalities involved in

  16. Incompressibility of asymmetric nuclear matter

    International Nuclear Information System (INIS)

    Chen, Liewen; Cai, Baojun; Shen, Chun; Ko, Cheming; Xu, Jun; Li, Baoan

    2010-01-01

    Using an isospin- and momentum-dependent modified Gogny (MDI) interaction, the Skyrme-Hartree-Fock (SHF) approach, and a phenomenological modified Skyrme-like (MSL) model, we have studied the incompressibility K sat (δ) of isospin asymmetric nuclear matter at its saturation density. Our results show that in the expansion of K sat (δ) in powers of isospin asymmetry δ, i.e., K sat (δ) = K 0 + K sat,2 δ 2 + K sat,4 δ 4 + O(δ 6 ), the magnitude of the 4th-order K sat,4 parameter is generally small. The 2nd-order K sat,2 parameter thus essentially characterizes the isospin dependence of the incompressibility of asymmetric nuclear matter at saturation density. Furthermore, the K sat,2 can be expressed as K sat,2 = K sym – 6L – J 0 /K 0 L in terms of the slope parameter L and the curvature parameter K sym of the symmetry energy and the third-order derivative parameter J 0 of the energy of symmetric nuclear matter at saturation density, and we find the higher order J 0 contribution to K sat,2 generally cannot be neglected. Also, we have found a linear correlation between K sym and L as well as between J 0 /K 0 and K 0 . Using these correlations together with the empirical constraints on K 0 and L, the nuclear symmetry energy E sym (ρ0) at normal nuclear density, and the nucleon effective mass, we have obtained an estimated value of K sat,2 = -370 ± 120 MeV for the 2nd-order parameter in the isospin asymmetry expansion of the incompressibility of asymmetric nuclear matter at its saturation density. (author)

  17. Treatment outcome of bimaxillary surgery for asymmetric skeletal class II deformity.

    Science.gov (United States)

    Chen, Yun-Fang; Liao, Yu-Fang; Chen, Yin-An; Chen, Yu-Ray

    2018-05-04

    Facial asymmetry is one of the main concerns in patients with a dentofacial deformity. The aims of the study were to (1) evaluate the changes in facial asymmetry after bimaxillary surgery for asymmetric skeletal class II deformity and (2) compare preoperative and postoperative facial asymmetry of class II patients with normal controls. The facial asymmetry was assessed for 30 adults (21 women and 9 men, mean age: 29.3 years) who consecutively underwent bimaxillary surgery for asymmetric skeletal class II deformity using cone-beam computed tomography before and at least 6 months after surgery. Thirty soft tissue and two dental landmarks were identified on each three-dimensional facial image, and the asymmetry index of each landmark was calculated. Results were compared with those of 30 normal control subjects (21 women and 9 men, mean age: 26.2 years) with skeletal class I structure. Six months after surgery, the asymmetric index of the lower face and total face decreased significantly (17.8 ± 29.4 and 16.6 ± 29.5 mm, respectively, both p class II patients had residual chin asymmetry. The postoperative total face asymmetric index was positively correlated with the preoperative asymmetric index (r = 0.37, p class II deformity resulted in a significant improvement in lower face asymmetry. However, approximately 50% of the patients still had residual chin asymmetry. The total face postoperative asymmetry was moderately related to the initial severity of asymmetry. These findings could help clinicians better understand orthognathic outcomes on different facial regions for patients with asymmetric class II deformity.

  18. The Impacts of Dry Dynamic Cores on Asymmetric Hurricane Intensification

    Science.gov (United States)

    Guimond, Stephen R.; Reisner, Jon M.; Marras, Simone; Giraldo, Francis X.

    2016-01-01

    The fundamental pathways for tropical cyclone (TC) intensification are explored by considering axisymmetric and asymmetric impulsive thermal perturbations to balanced, TC-like vortices using the dynamic cores of three different nonlinear numerical models. Attempts at reproducing the results of previous work, which used the community WRF Model, revealed a discrepancy with the impacts of purely asymmetric thermal forcing. The current study finds that thermal asymmetries can have an important, largely positive role on the vortex intensification, whereas other studies find that asymmetric impacts are negligible. Analysis of the spectral energetics of each numerical model indicates that the vortex response to asymmetric thermal perturbations is significantly damped in WRF relative to the other models. Spectral kinetic energy budgets show that this anomalous damping is primarily due to the increased removal of kinetic energy from the vertical divergence of the vertical pressure flux, which is related to the flux of inertia-gravity wave energy. The increased kinetic energy in the other two models is shown to originate around the scales of the heating and propagate upscale with time from nonlinear effects. For very large thermal amplitudes (50 K), the anomalous removal of kinetic energy due to inertia-gravity wave activity is much smaller, resulting in good agreement between models. The results of this paper indicate that the numerical treatment of small-scale processes that project strongly onto inertia-gravity wave energy can lead to significant differences in asymmetric TC intensification. Sensitivity tests with different time integration schemes suggest that diffusion entering into the implicit solution procedure is partly responsible for the anomalous damping of energy.

  19. High power CW output from low confinement asymmetric structure diode laser

    NARCIS (Netherlands)

    Iordache, G.; Buda, M.; Acket, G.A.; Roer, van de T.G.; Kaufmann, L.M.F.; Karouta, F.; Jagadish, C.; Tan, H.H.

    1999-01-01

    High power continuous wave output from diode lasers using low loss, low confinement, asymmetric structures is demonstrated. An asymmetric structure with an optical trap layer was grown by metal organic vapour phase epitaxy. Gain guided 50 µm wide stripe 1-3 mm long diode lasers were studied. 1.8 W

  20. Asymmetric statistical features of the Chinese domestic and international gold price fluctuation

    Science.gov (United States)

    Cao, Guangxi; Zhao, Yingchao; Han, Yan

    2015-05-01

    Analyzing the statistical features of fluctuation is remarkably significant for financial risk identification and measurement. In this study, the asymmetric detrended fluctuation analysis (A-DFA) method was applied to evaluate asymmetric multifractal scaling behaviors in the Shanghai and New York gold markets. Our findings showed that the multifractal features of the Chinese and international gold spot markets were asymmetric. The gold return series persisted longer in an increasing trend than in a decreasing trend. Moreover, the asymmetric degree of multifractals in the Chinese and international gold markets decreased with the increase in fluctuation range. In addition, the empirical analysis using sliding window technology indicated that multifractal asymmetry in the Chinese and international gold markets was characterized by its time-varying feature. However, the Shanghai and international gold markets basically shared a similar asymmetric degree evolution pattern. The American subprime mortgage crisis (2008) and the European debt crisis (2010) enhanced the asymmetric degree of the multifractal features of the Chinese and international gold markets. Furthermore, we also make statistical tests for the results of multifractatity and asymmetry, and discuss the origin of them. Finally, results of the empirical analysis using the threshold autoregressive conditional heteroskedasticity (TARCH) and exponential generalized autoregressive conditional heteroskedasticity (EGARCH) models exhibited that good news had a more significant effect on the cyclical fluctuation of the gold market than bad news. Moreover, good news exerted a more significant effect on the Chinese gold market than on the international gold market.

  1. Analysis of Surface Plasmon Resonance Curves with a Novel Sigmoid-Asymmetric Fitting Algorithm

    Directory of Open Access Journals (Sweden)

    Daeho Jang

    2015-09-01

    Full Text Available The present study introduces a novel curve-fitting algorithm for surface plasmon resonance (SPR curves using a self-constructed, wedge-shaped beam type angular interrogation SPR spectroscopy technique. Previous fitting approaches such as asymmetric and polynomial equations are still unsatisfactory for analyzing full SPR curves and their use is limited to determining the resonance angle. In the present study, we developed a sigmoid-asymmetric equation that provides excellent curve-fitting for the whole SPR curve over a range of incident angles, including regions of the critical angle and resonance angle. Regardless of the bulk fluid type (i.e., water and air, the present sigmoid-asymmetric fitting exhibited nearly perfect matching with a full SPR curve, whereas the asymmetric and polynomial curve fitting methods did not. Because the present curve-fitting sigmoid-asymmetric equation can determine the critical angle as well as the resonance angle, the undesired effect caused by the bulk fluid refractive index was excluded by subtracting the critical angle from the resonance angle in real time. In conclusion, the proposed sigmoid-asymmetric curve-fitting algorithm for SPR curves is widely applicable to various SPR measurements, while excluding the effect of bulk fluids on the sensing layer.

  2. Cell chirality: its origin and roles in left-right asymmetric development.

    Science.gov (United States)

    Inaki, Mikiko; Liu, Jingyang; Matsuno, Kenji

    2016-12-19

    An item is chiral if it cannot be superimposed on its mirror image. Most biological molecules are chiral. The homochirality of amino acids ensures that proteins are chiral, which is essential for their functions. Chirality also occurs at the whole-cell level, which was first studied mostly in ciliates, single-celled protozoans. Ciliates show chirality in their cortical structures, which is not determined by genetics, but by 'cortical inheritance'. These studies suggested that molecular chirality directs whole-cell chirality. Intriguingly, chirality in cellular structures and functions is also found in metazoans. In Drosophila, intrinsic cell chirality is observed in various left-right (LR) asymmetric tissues, and appears to be responsible for their LR asymmetric morphogenesis. In other invertebrates, such as snails and Caenorhabditis elegans, blastomere chirality is responsible for subsequent LR asymmetric development. Various cultured cells of vertebrates also show intrinsic chirality in their cellular behaviours and intracellular structural dynamics. Thus, cell chirality may be a general property of eukaryotic cells. In Drosophila, cell chirality drives the LR asymmetric development of individual organs, without establishing the LR axis of the whole embryo. Considering that organ-intrinsic LR asymmetry is also reported in vertebrates, this mechanism may contribute to LR asymmetric development across phyla.This article is part of the themed issue 'Provocative questions in left-right asymmetry'. © 2016 The Authors.

  3. Cell chirality: its origin and roles in left–right asymmetric development

    Science.gov (United States)

    Inaki, Mikiko; Liu, Jingyang

    2016-01-01

    An item is chiral if it cannot be superimposed on its mirror image. Most biological molecules are chiral. The homochirality of amino acids ensures that proteins are chiral, which is essential for their functions. Chirality also occurs at the whole-cell level, which was first studied mostly in ciliates, single-celled protozoans. Ciliates show chirality in their cortical structures, which is not determined by genetics, but by ‘cortical inheritance’. These studies suggested that molecular chirality directs whole-cell chirality. Intriguingly, chirality in cellular structures and functions is also found in metazoans. In Drosophila, intrinsic cell chirality is observed in various left–right (LR) asymmetric tissues, and appears to be responsible for their LR asymmetric morphogenesis. In other invertebrates, such as snails and Caenorhabditis elegans, blastomere chirality is responsible for subsequent LR asymmetric development. Various cultured cells of vertebrates also show intrinsic chirality in their cellular behaviours and intracellular structural dynamics. Thus, cell chirality may be a general property of eukaryotic cells. In Drosophila, cell chirality drives the LR asymmetric development of individual organs, without establishing the LR axis of the whole embryo. Considering that organ-intrinsic LR asymmetry is also reported in vertebrates, this mechanism may contribute to LR asymmetric development across phyla. This article is part of the themed issue ‘Provocative questions in left–right asymmetry’. PMID:27821533

  4. Orientation- and position-controlled alignment of asymmetric silicon microrod on a substrate with asymmetric electrodes

    Science.gov (United States)

    Shibata, Akihide; Watanabe, Keiji; Sato, Takuya; Kotaki, Hiroshi; Schuele, Paul J.; Crowder, Mark A.; Zhan, Changqing; Hartzell, John W.; Nakatani, Ryoichi

    2014-03-01

    In this paper, we demonstrate the orientation-controlled alignment of asymmetric Si microrods on a glass substrate with an asymmetric pair of electrodes. The Si microrods have the shape of a paddle with a blade and a shaft part, and the pair of electrodes consists of a narrow electrode and a wide electrode. By applying AC bias to the electrodes, the Si microrods suspended in a fluid align in such a way to settle across the electrode pair, and over 80% of the aligned Si microrods have an orientation with the blade and the shaft of the paddle on the wide and the narrow electrodes, respectively. When Si microrods have a shell of dielectric film and its thickness on the top face is thicker than that on the bottom face, 97.8% of the Si microrods are aligned with the top face facing upwards. This technique is useful for orientation-controlled alignment of nano- and microsized devices that have polarity or a distinction between the top and bottom faces.

  5. Electromagnetic resonance in the asymmetric terahertz metamaterials with triangle microstructure

    Science.gov (United States)

    Xing, Yuanyuan; Zhang, Xiaoyu; Zhang, Qiang; Gu, Yanping; Qian, Yunan; Lin, Xingyue; Tang, Yunhai; Cheng, Xinli; Qin, Changfa; Shen, Jiaoyan; Zang, Taocheng; Ma, Chunlan

    2018-05-01

    We investigate terahertz transmission properties and electromagnetic resonance modes in the asymmetric triangle structures with the change of asymmetric distance and the direction of electric field. When the THz electric field is perpendicular to the split gap of triangle, the electric field can better excite the THz absorption in the triangle structures. Importantly, electromagnetically induced transparency (EIT) characteristics are observed in the triangle structures due to the destructive interference of the different excited modes. The distributions of electric field and surface current density simulated by finite difference time domain indicate that the bright mode is excited by the side of triangle structures and dark mode is excited by the gap-side of triangle. The present study is helpful to understand the electromagnetic resonance in the asymmetric triangular metamaterials.

  6. Asymmetric adsorption of alanine by quartz powder from ethanol solution

    Energy Technology Data Exchange (ETDEWEB)

    Furuyama, Shozo; Sawada, Michio; Hachiya, Kinji; Morimoto, Tetsuo (Okayama Univ. (Japan). Faculty of Science)

    1982-11-01

    The asymmetric adsorption of the racemic alanine by the optically active quartz from ethanol solution at 8/sup 0/C was studied by the /sup 14/C-tracer method and the newly developed /sup 14/C-tracer ninhydrin-colorimetry combination method. The preferential adsorption of L-alanine by levorotatory quartz (l-quartz) and D-alanine by dextrorotatory quartz (d-quartz) was confirmed. The asymmetric adsorptivity (Asub(s)) falls in the range of 1.1 - 1.3, which is comparable with the value determined at - 80/sup 0/C in the previous paper. The effects of water content in the ethanol solution and of the adsorption temperature upon the adsorption affinity of alanine to quartz were also measured. The cause for the asymmetric adsorption is discussed from the crystallographic point of view.

  7. Brownian Motion of Asymmetric Boomerang Colloidal Particles

    Science.gov (United States)

    Chakrabarty, Ayan; Konya, Andrew; Wang, Feng; Selinger, Jonathan; Sun, Kai; Wei, Qi-Huo

    2014-03-01

    We used video microscopy and single particle tracking to study the diffusion and local behaviors of asymmetric boomerang particles in a quasi-two dimensional geometry. The motion is biased towards the center of hydrodynamic stress (CoH) and the mean square displacements of the particles are linear at short and long times with different diffusion coefficients and in the crossover regime it is sub-diffusive. Our model based on Langevin theory shows that these behaviors arise from the non-coincidence of the CoH with the center of the body. Since asymmetric boomerangs represent a class of rigid bodies of more generals shape, therefore our findings are generic and true for any non-skewed particle in two dimensions. Both experimental and theoretical results will be discussed.

  8. The synchronization of asymmetric-structured electric coupling neuronal system

    Science.gov (United States)

    Wang, Guanping; Jin, Wuyin; Liu, Hao; Sun, Wei

    2018-02-01

    Based on the Hindmarsh-Rose (HR) model, the synchronization dynamics of asymmetric-structured electric coupling two neuronal system is investigated in this paper. It is discovered that when the time-delay scope and coupling strength for the synchronization are correlated positively under unequal time delay, the time-delay difference does not make a clear distinction between the two individual inter-spike intervals (ISI) bifurcation diagrams of the two coupled neurons. Therefore, the superficial difference of the system synchronization dynamics is not obvious for the unequal time-delay feedback. In the asymmetrical current incentives under asymmetric electric coupled system, the two neurons can only be almost completely synchronized in specific area of the interval which end-pointed with two discharge modes for a single neuron under different stimuli currents before coupling, but the intervention of time-delay feedback, together with the change of the coupling strength, can make the coupled system not only almost completely synchronized within anywhere in the front area, but also outside of it.

  9. Examining Theories of Distributive Justice with an Asymmetric Public Goods Game

    Science.gov (United States)

    Schmidt, Stephen J.

    2015-01-01

    In this article, the author presents an asymmetric version of the familiar public goods classroom experiment, in which some players are given more tokens to invest than others, and players collectively decide whether to divide the return to the group investment asymmetrically as well. The asymmetry between players raises normative issues about…

  10. Asymmetric Membranes Containing Micron-Size Silicon for High Performance Lithium Ion Battery Anode

    International Nuclear Information System (INIS)

    Byrd, Ian; Wu, Ji

    2016-01-01

    Micron-size Si anode is notorious for having extremely poor cycle life. It is mainly caused by the large volume change (∼300%) and poor mechanical strength of the Si electrode. Satisfying methods to address this issue are seriously lacking in literature. In this study, novel single-layer, double-layer and triple-layer asymmetric membranes containing micron-size silicon have been fabricated using a simple phase inversion method to dramatically improve its cyclability. The electrochemical performance of these asymmetric membranes as lithium ion battery anodes are evaluated and compared to pure micron-size Si powders and carbonaceous asymmetric membranes. All three types of asymmetric membrane electrodes demonstrate significantly enhanced stability as compared to pure Si powders. The single-layer asymmetric membrane has the largest capacity degradation due to the loss of pulverized Si powders from the membrane surface, only 40% of whose capacity can be retained in 100 cycles. But this performance is still much better than pure micron-size silicon electrode. After being coated with nanoporous carbonaceous layers on both sides of a single-layer asymmetric membrane to make a triple-layer asymmetric membrane (sandwich structure), the capacity retention is notably increased to 88% in 100 cycles at 610 mAh g"−"1 and 0.5C. The enhanced stability is attributed to the extra nanoporous coatings that can prevent the fractured Si powders from being leached out and allow facile lithium ion diffusions. Such a novel, efficient and scalable method may provide beneficiary guidance for designing high capacity lithium ion battery anodes with large volume change issues.

  11. Effect of radiation and magnetic field on peristaltic transport of nanofluids through a porous space in a tapered asymmetric channel

    Energy Technology Data Exchange (ETDEWEB)

    Kothandapani, M., E-mail: mkothandapani@gmail.com [Department of Mathematics, University College of Engineering Arni, (A Constituent College of Anna University Chennai), Arni 632326, Tamil Nadu (India); Prakash, J., E-mail: prakashjayavel@yahoo.co.in [Department of Mathematics, Arulmigu Meenakshi Amman College of Engineering, Vadamavandal 604410, Tamil Nadu (India)

    2015-03-15

    Theoretical analyses on the effect of radiation and MHD on the peristaltic flow of a nanofluid through a porous medium in a two dimensional tapered asymmetric channel has been made. The nanofluid is assumed to be electrically conducting in the presence of a uniform magnetic field. The transport equation accounts the both Brownian motion and thermophoresis along with the radiation reaction. The problem has been further simplified with the authentic assumptions of long wavelength and small Reynolds number. The analytical expressions obtained for the axial velocity, stream function, temperature field, nanoparticle fraction field and pressure gradient provide satisfactory explanation. Influence of various parameters on the flow characteristics have been discussed with the help of graphical results. The trapping phenomenon has also been discussed in detail. - Highlights: • Combine effect of thermal radiation and MHD on the peristaltic flow of a Newtonian nanofluid are discussed. • This work may be first attempt dealing the study of Newtonian nanofluid flow in the porous tapered asymmetric channel. • The velocity, stream function, temperature field and nanoparticle fraction field provide satisfactory explanation with help of graphs.

  12. A method of the asymmetric Abel's inversion in plasma diagnosis

    International Nuclear Information System (INIS)

    Matoba, Tohru; Funahashi, Akimasa

    1975-09-01

    In the case of a noncylindrical plasma, axis symmetric components are drawn from observed projected intensities of physical quantities, assuming an asymmetric form. And the radial intensity distribution is determined by Abel's inversion method. The best fitting curve is obtained analytically from measured values by the least-square estimation of nonlinear parameters. The cylindrical symmetric Abel's inversion code ( ABELIC ) and the asymmetric Abel's inversion code ( ABELILSENP 2 ) are described. (auth.)

  13. Fluorescent nanohybrids based on asymmetrical cyanine dyes decorated carbon nanotubes

    OpenAIRE

    Çavuşlar, Özge; Cavuslar, Ozge

    2015-01-01

    In this thesis, we focused on imparting new optical properties to carbon nanotubes (CNTs) to allow their optical detection and visualization in biomedical applications. We investigated the interactions of CNTs and DNA wrapped CNTs with asymmetrical cyanine dye molecules to study the applicability of resulting hybrid materials to fluorescent based systems. When CNTs interacted with asymmetrical cyanine dyes, they constructed a light absorbing nanoarray. However, the fluorescence emission of th...

  14. Asymmetric-shell ignition capsule design to tune the low-mode asymmetry during the peak drive

    International Nuclear Information System (INIS)

    Gu, Jianfa; Dai, Zhensheng; Song, Peng; Zou, Shiyang; Ye, Wenhua; Zheng, Wudi; Gu, Peijun; Wang, Jianguo; Zhu, Shaoping

    2016-01-01

    The low-mode radiation flux asymmetry in the hohlraum is a main source of performance degradation in the National Ignition Facility (NIF) implosion experiments. To counteract the deleterious effects of the large positive P2 flux asymmetry during the peak drive, this paper develops a new tuning method called asymmetric-shell ignition capsule design which adopts the intentionally asymmetric CH ablator layer or deuterium-tritium (DT) ice layer. A series of two-dimensional implosion simulations have been performed, and the results show that the intentionally asymmetric DT ice layer can significantly improve the fuel ρR symmetry, hot spot shape, hot spot internal energy, and the final neutron yield compared to the spherical capsule. This indicates that the DT asymmetric-shell capsule design is an effective tuning method, while the CH ablator asymmetric-shell capsule could not correct the fuel ρR asymmetry, and it is not as effective as the DT asymmetric-shell capsule design.

  15. Asymmetric-shell ignition capsule design to tune the low-mode asymmetry during the peak drive

    Science.gov (United States)

    Gu, Jianfa; Dai, Zhensheng; Song, Peng; Zou, Shiyang; Ye, Wenhua; Zheng, Wudi; Gu, Peijun; Wang, Jianguo; Zhu, Shaoping

    2016-08-01

    The low-mode radiation flux asymmetry in the hohlraum is a main source of performance degradation in the National Ignition Facility (NIF) implosion experiments. To counteract the deleterious effects of the large positive P2 flux asymmetry during the peak drive, this paper develops a new tuning method called asymmetric-shell ignition capsule design which adopts the intentionally asymmetric CH ablator layer or deuterium-tritium (DT) ice layer. A series of two-dimensional implosion simulations have been performed, and the results show that the intentionally asymmetric DT ice layer can significantly improve the fuel ρR symmetry, hot spot shape, hot spot internal energy, and the final neutron yield compared to the spherical capsule. This indicates that the DT asymmetric-shell capsule design is an effective tuning method, while the CH ablator asymmetric-shell capsule could not correct the fuel ρR asymmetry, and it is not as effective as the DT asymmetric-shell capsule design.

  16. Asymmetric-shell ignition capsule design to tune the low-mode asymmetry during the peak drive

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Jianfa, E-mail: gu-jianfa@iapcm.ac.cn; Dai, Zhensheng, E-mail: dai-zhensheng@iapcm.ac.cn; Song, Peng; Zou, Shiyang; Ye, Wenhua; Zheng, Wudi; Gu, Peijun; Wang, Jianguo; Zhu, Shaoping [Institute of Applied Physics and Computational Mathematics, Beijing 100088 (China)

    2016-08-15

    The low-mode radiation flux asymmetry in the hohlraum is a main source of performance degradation in the National Ignition Facility (NIF) implosion experiments. To counteract the deleterious effects of the large positive P2 flux asymmetry during the peak drive, this paper develops a new tuning method called asymmetric-shell ignition capsule design which adopts the intentionally asymmetric CH ablator layer or deuterium-tritium (DT) ice layer. A series of two-dimensional implosion simulations have been performed, and the results show that the intentionally asymmetric DT ice layer can significantly improve the fuel ρR symmetry, hot spot shape, hot spot internal energy, and the final neutron yield compared to the spherical capsule. This indicates that the DT asymmetric-shell capsule design is an effective tuning method, while the CH ablator asymmetric-shell capsule could not correct the fuel ρR asymmetry, and it is not as effective as the DT asymmetric-shell capsule design.

  17. Asymmetric dark matter annihilation as a test of non-standard cosmologies

    International Nuclear Information System (INIS)

    Gelmini, Graciela B.; Huh, Ji-Haeng; Rehagen, Thomas

    2013-01-01

    We show that the relic abundance of the minority component of asymmetric dark matter can be very sensitive to the expansion rate of the Universe and the temperature of transition between a non-standard pre-Big Bang Nucleosynthesis cosmological phase and the standard radiation dominated phase, if chemical decoupling happens before this transition. In particular, because the annihilation cross section of asymmetric dark matter is typically larger than that of symmetric dark matter in the standard cosmology, the decrease in relic density of the minority component in non-standard cosmologies with respect to the majority component may be compensated by the increase in annihilation cross section, so that the annihilation rate at present of asymmetric dark matter, contrary to general belief, could be larger than that of symmetric dark matter in the standard cosmology. Thus, if the annihilation cross section of the asymmetric dark matter candidate is known, the annihilation rate at present, if detectable, could be used to test the Universe before Big Bang Nucleosynthesis, an epoch from which we do not yet have any data

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

    KAUST Repository

    Zhu, Bo

    2015-12-09

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

  19. Asymmetric information and economics

    Science.gov (United States)

    Frieden, B. Roy; Hawkins, Raymond J.

    2010-01-01

    We present an expression of the economic concept of asymmetric information with which it is possible to derive the dynamical laws of an economy. To illustrate the utility of this approach we show how the assumption of optimal information flow leads to a general class of investment strategies including the well-known Q theory of Tobin. Novel consequences of this formalism include a natural definition of market efficiency and an uncertainty principle relating capital stock and investment flow.

  20. Component-Level Demonstration of a Microfabricated Atomic Frequency Reference

    Science.gov (United States)

    2005-08-01

    Kitching, L. A. Liew, and J. Moreland, "A microfabricated atomic clock," Applied Physics Letters, vol. 85, pp. 1460-1462, 2004. [4] R. Lutwak , P...Symposium on Frequency Standards and Metrology, P. Gill, Ed. St. Andrews, Scotland: World Scientific, 2001, pp. 155-166. [31] R. Lutwak , D. Emmons...Frequency and Time Forum. Tampa, FL, 2003, pp. 31-32. [71] R. Lutwak , D. Emmons, T. English, W. Riley, A. Duwel, M. Varghese, D. K. Serkland, and

  1. The Chip-Scale Atomic Clock - Low-Power Physics Package

    Science.gov (United States)

    2004-12-01

    36th Annual Precise Time and Time Interval (PTTI) Meeting 339 THE CHIP-SCALE ATOMIC CLOCK – LOW-POWER PHYSICS PACKAGE R. Lutwak ...pdf/documents/ds-x72.pdf [2] R. Lutwak , D. Emmons, W. Riley, and R. M. Garvey, 2003, “The Chip-Scale Atomic Clock – Coherent Population Trapping vs...2002, Reston, Virginia, USA (U.S. Naval Observatory, Washington, D.C.), pp. 539-550. [3] R. Lutwak , D. Emmons, T. English, and W. Riley, 2004

  2. Thomson scattering measurements from asymmetric interpenetrating plasma flows

    Energy Technology Data Exchange (ETDEWEB)

    Ross, J. S., E-mail: ross36@llnl.gov; Moody, J. D.; Fiuza, F.; Ryutov, D.; Divol, L.; Huntington, C. M.; Park, H.-S. [Lawrence Livermore National Laboratory, P.O. Box 808, Livermore, California 94551 (United States)

    2014-11-15

    Imaging Thomson scattering measurements of collective ion-acoustic fluctuations have been utilized to determine ion temperature and density from laser produced counter-streaming asymmetric flows. Two foils are heated with 8 laser beams each, 500 J per beam, at the Omega Laser facility. Measurements are made 4 mm from the foil surface using a 60 J 2ω probe laser with a 200 ps pulse length. Measuring the electron density and temperature from the electron-plasma fluctuations constrains the fit of the multi-ion species, asymmetric flows theoretical form factor for the ion feature such that the ion temperatures, ion densities, and flow velocities for each plasma flow are determined.

  3. Decoding Pure Rotational Molecular Spectra for Asymmetric Molecules

    Directory of Open Access Journals (Sweden)

    S. A. Cooke

    2013-01-01

    Full Text Available Rotational spectroscopy can provide insights of unparalleled precision with respect to the wavefunctions of molecular systems that have relevance in fields as diverse as astronomy and biology. In this paper, we demonstrate how asymmetric molecular pure rotational spectra may be analyzed “pictorially” and with simple formulae. It is shown that the interpretation of such spectra relies heavily upon pattern recognition. The presentation of some common spectral line positions in near-prolate asymmetric rotational spectra provides a means by which spectral assignment, and approximate rotational constant determination, may be usefully explored. To aid in this endeavor we have created a supporting, free, web page and mobile web page.

  4. Finite stage asymmetric repeated games: Both players' viewpoints

    KAUST Repository

    Li, Lichun

    2017-01-05

    In asymmetric zero-sum games, one player has superior information about the game over the other. It is known that the informed players (maximizer) face the tradeoff of exploiting its superior information at the cost of revealing its superior information, but the basic point of the uninformed player (minimizer)\\'s decision making remains unknown. This paper studies the finite stage asymmetric repeated games from both players\\' viewpoints, and derives that not only security strategies but also the opponents\\' corresponding best responses depends only on the informed player\\'s history action sequences. Moreover, efficient LP formulations to compute both player\\'s security strategies are provided.

  5. Simulation of seismic signals from asymmetric LANL hydrodynamic calculations

    International Nuclear Information System (INIS)

    Stevens, J.L.; Rimer, N.; Halda, E.J.; Barker, T.G.; Davis, C.G.; Johnson, W.E.

    1993-01-01

    Hydrodynamic calculations of an asymmetric nuclear explosion source were propagated to teleseismic distances to investigate the effects of the asymmetric source on seismic signals. The source is an explosion in a 12 meter long canister with the device at one end of the canister and a metal plate adjacent to the explosion. This produces a strongly asymmetric two-lobed source in the hydrodynamic region. The hydrodynamic source is propagated to the far field using a three-step process. The Eulerian hydrodynamic code SOIL was used by LANL to calculate the material velocity, density, and internal energy up to a time of 8.9 milliseconds after the explosion. These quantities were then transferred to an initial grid for the Lagrangian elastic/plastic finite difference code CRAM, which was used by S-CUBED to propagate the signal through the region of nonlinear deformation into the external elastic region. The cavity size and shape at the time of the overlay were determined by searching for a rapid density change in the SOIL grid, and this interior region was then rezoned into a single zone. The CRAM calculation includes material strength and gravity, and includes the effect of the free surface above the explosion. Finally, far field body waves were calculated by integrating over a closed surface in the elastic region and using the representation theorem. A second calculation was performed using an initially spherical source for comparison with the asymmetric calculation

  6. Clinical characteristics in patients with asymmetric idiopathic pulmonary fibrosis.

    Science.gov (United States)

    Callahan, Sean J; Xia, Meng; Murray, Susan; Flaherty, Kevin R

    2016-10-01

    A group of patients with idiopathic pulmonary fibrosis (IPF) presents with disease affecting one lung markedly more than the other. At this time, it is unclear how this population differs from those who present with more symmetric disease. We sought to explain the characteristics of the asymmetric group and how their disease progresses. In this retrospective case-control study we accessed an interstitial lung disease (ILD) database and identified 14 asymmetric IPF cases via high-resolution computed tomography (HRCT) scoring of each lung lobe's disease severity. We identified 28 symmetric IPF controls from the same database using the same methods, and compared the clinical features of each group. Patients with asymmetric disease exhibited similar demographics as those in the general IPF population; they were predominantly male (64%), elderly (69 years old), and used tobacco (57%). We found a trend toward significantly increased all-cause mortality in the case population two years following diagnosis (p = 0.089). Pulmonary function tests were significantly lower in the case group at the time of diagnosis, then both groups experienced gradual decline. We found no statistically significant differences in number of IPF exacerbations (cases 43%, controls 39%, p = 0.824) and gastro-esophageal reflux (both groups 50%). Patients with asymmetric IPF resemble patients in the general IPF population but may have a lower overall survival rate. Further systemic factors may be studied to identify reasons for disease asymmetry and clinical decline in this population. Published by Elsevier Ltd.

  7. Broadband chirality and asymmetric transmission in ultrathin 90°-twisted Babinet-inverted metasurfaces

    Science.gov (United States)

    Shi, J. H.; Ma, H. F.; Guan, C. Y.; Wang, Z. P.; Cui, T. J.

    2014-04-01

    A broadband asymmetric transmission of linearly polarized waves with totally suppressed copolarization transmission is experimentally demonstrated in ultrathin 90°-twisted Babinet-inverted metasurfaces constructed by an array of asymmetrically split ring apertures. The only accessible direction-dependent cross-polarization transmission is allowed in this anisotropic chiral metamaterial. Through full-wave simulation and experiment results, the bilayered Babinet-inverted metasurface reveals broadband artificial chirality and asymmetric transmission, with a transmission contrast that is better than 17.7 dB within a 50% relative bandwidth for two opposite directions. In particular, we can modify polarization conversion efficiency and the bandwidth of asymmetric transmission via parametric study.

  8. Quantum computation in semiconductor quantum dots of electron-spin asymmetric anisotropic exchange

    International Nuclear Information System (INIS)

    Hao Xiang; Zhu Shiqun

    2007-01-01

    The universal quantum computation is obtained when there exists asymmetric anisotropic exchange between electron spins in coupled semiconductor quantum dots. The asymmetric Heisenberg model can be transformed into the isotropic model through the control of two local unitary rotations for the realization of essential quantum gates. The rotations on each qubit are symmetrical and depend on the strength and orientation of asymmetric exchange. The implementation of the axially symmetric local magnetic fields can assist the construction of quantum logic gates in anisotropic coupled quantum dots. This proposal can efficiently use each physical electron spin as a logical qubit in the universal quantum computation

  9. Organocatalytic Asymmetric Michael Addition of 4-Hydroxycoumarin to β,γ-Unsaturated α-Keto Esters

    Energy Technology Data Exchange (ETDEWEB)

    Suh, Chang Won; Han, Tae Hyun; Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

    2013-06-15

    In conclusion, we have developed organocatalytic enantioselective conjugate addition reaction of 4-hydroxycoumarin (1) to β,γ-unsaturated α-keto esters 2 to afford biologically valuable warfarin derivatives 3. The process is efficiently catalyzed by a binaphthyl-modified thiourea organocatalyst. The coumarin core is present as a characteristic structural motif in a large number of natural products and biologically active molecules.1 Particularly, many of these naturally occurring 4-hydroxycoumarin and their synthetic analogues are important precursors for the synthesis of natural products and pharmaceuticals. Enantioselective organocatalytic conjugate addition of 4-hydroxycoumarin to α,β-unsaturated ketones is a straightforward method to access warfarin which is an effective anticoagulants. Although a number of reactions of α,β-unsaturated ketones as Michael acceptors have been reported, the corresponding β,γ-unsaturated α-keto esters have received relatively little attention as Michael acceptors. Recently, several groups have reported the asymmetric Michael addition of 4-hydroxycoumarin to β,γ-unsaturated α-keto esters catalyzed by Cu(II)-bisoxazoline, N,N'-dioxide-Ni(II) complexes, thiourea catalysts. Although several efficient methods have been achieved by these systems, an effective method for the synthesis of warfarin analogues is still a challenge.

  10. Organocatalytic Asymmetric Michael Addition of 4-Hydroxycoumarin to β,γ-Unsaturated α-Keto Esters

    International Nuclear Information System (INIS)

    Suh, Chang Won; Han, Tae Hyun; Kim, Dae Young

    2013-01-01

    In conclusion, we have developed organocatalytic enantioselective conjugate addition reaction of 4-hydroxycoumarin (1) to β,γ-unsaturated α-keto esters 2 to afford biologically valuable warfarin derivatives 3. The process is efficiently catalyzed by a binaphthyl-modified thiourea organocatalyst. The coumarin core is present as a characteristic structural motif in a large number of natural products and biologically active molecules.1 Particularly, many of these naturally occurring 4-hydroxycoumarin and their synthetic analogues are important precursors for the synthesis of natural products and pharmaceuticals. Enantioselective organocatalytic conjugate addition of 4-hydroxycoumarin to α,β-unsaturated ketones is a straightforward method to access warfarin which is an effective anticoagulants. Although a number of reactions of α,β-unsaturated ketones as Michael acceptors have been reported, the corresponding β,γ-unsaturated α-keto esters have received relatively little attention as Michael acceptors. Recently, several groups have reported the asymmetric Michael addition of 4-hydroxycoumarin to β,γ-unsaturated α-keto esters catalyzed by Cu(II)-bisoxazoline, N,N'-dioxide-Ni(II) complexes, thiourea catalysts. Although several efficient methods have been achieved by these systems, an effective method for the synthesis of warfarin analogues is still a challenge

  11. Asymmetrical Representation of Gender in Amharic1

    African Journals Online (AJOL)

    Administrator

    in its grammar. Gender representation in this language is asymmetrical heavily ..... In dictionaries where. Amharic appears either as the target or the source language, verbs are entered ...... The Dialects of Amharic Revisited. Semitica et.

  12. Asymmetric multi-fractality in the U.S. stock indices using index-based model of A-MFDFA

    International Nuclear Information System (INIS)

    Lee, Minhyuk; Song, Jae Wook; Park, Ji Hwan; Chang, Woojin

    2017-01-01

    Highlights: • ‘Index-based A-MFDFA’ model is proposed to assess the asymmetric multi-fractality. • The asymmetric multi-fractality in the U.S. stock indices are investigated using ‘Index-based’ and ‘Return-based’ A-MFDFA. • The asymmetric feature is more significantly identified by ‘Index-based’ model than ‘return-based’ model. • Source of multi-fractality and time-varying features are analyzed. - Abstract: We detect the asymmetric multi-fractality in the U.S. stock indices based on the asymmetric multi-fractal detrended fluctuation analysis (A-MFDFA). Instead using the conventional return-based approach, we propose the index-based model of A-MFDFA where the trend based on the evolution of stock index rather than stock price return plays a role for evaluating the asymmetric scaling behaviors. The results show that the multi-fractal behaviors of the U.S. stock indices are asymmetric and the index-based model detects the asymmetric multi-fractality better than return-based model. We also discuss the source of multi-fractality and its asymmetry and observe that the multi-fractal asymmetry in the U.S. stock indices has a time-varying feature where the degree of multi-fractality and asymmetry increase during the financial crisis.

  13. Asymmetric quantum cloning machines

    International Nuclear Information System (INIS)

    Cerf, N.J.

    1998-01-01

    A family of asymmetric cloning machines for quantum bits and N-dimensional quantum states is introduced. These machines produce two approximate copies of a single quantum state that emerge from two distinct channels. In particular, an asymmetric Pauli cloning machine is defined that makes two imperfect copies of a quantum bit, while the overall input-to-output operation for each copy is a Pauli channel. A no-cloning inequality is derived, characterizing the impossibility of copying imposed by quantum mechanics. If p and p ' are the probabilities of the depolarizing channels associated with the two outputs, the domain in (√p,√p ' )-space located inside a particular ellipse representing close-to-perfect cloning is forbidden. This ellipse tends to a circle when copying an N-dimensional state with N→∞, which has a simple semi-classical interpretation. The symmetric Pauli cloning machines are then used to provide an upper bound on the quantum capacity of the Pauli channel of probabilities p x , p y and p z . The capacity is proven to be vanishing if (√p x , √p y , √p z ) lies outside an ellipsoid whose pole coincides with the depolarizing channel that underlies the universal cloning machine. Finally, the tradeoff between the quality of the two copies is shown to result from a complementarity akin to Heisenberg uncertainty principle. (author)

  14. Monte Carlo simulation of asymmetrical growth of cube-shaped nanoparticles

    International Nuclear Information System (INIS)

    Wang Yuanyuan; Xie Huaqing; Wu Zihua; Xing Jiaojiao

    2016-01-01

    We simulated the asymmetrical growth of cube-shaped nanoparticles by applying the Monte Carlo method. The influence of the specific mechanisms on the crystal growth of nanoparticles has been phenomenologically described by efficient growth possibilities along different directions (or crystal faces). The roles of the thermodynamic and kinetic factors have been evaluated in three phenomenological models. The simulation results would benefit the understanding about the cause and manner of the asymmetrical growth of nanoparticles. (paper)

  15. Copper(II)-catalyzed enantioselective hydrosilylation of halo-substituted alkyl aryl and heteroaryl ketones: asymmetric synthesis of (R)-fluoxetine and (S)-duloxetine.

    Science.gov (United States)

    Zhou, Ji-Ning; Fang, Qiang; Hu, Yi-Hu; Yang, Li-Yao; Wu, Fei-Fei; Xie, Lin-Jie; Wu, Jing; Li, Shijun

    2014-02-14

    A set of reaction conditions has been established to facilitate the non-precious copper-catalyzed enantioselective hydrosilylation of a number of structurally diverse β-, γ- or ε-halo-substituted alkyl aryl ketones and α-, β- or γ-halo-substituted alkyl heteroaryl ketones under air to afford a broad spectrum of halo alcohols in high yields and good to excellent enantioselectivities (up to 99% ee). The developed procedure has been successfully applied to the asymmetric synthesis of antidepressant drugs (R)-fluoxetine and (S)-duloxetine, which highlighted its synthetic utility.

  16. Highly enantio- and diastereoselective reactions of γ-substituted butenolides through direct vinylogous conjugate additions

    KAUST Repository

    Zhang, Wen; Tan, Davin; Lee, Richmond; Tong, Guanghu; Chen, Wenchao; Qi, Baojian; Huang, Kuo-Wei; Tan, Choonhong; Jiang, Zhiyong

    2012-01-01

    The strength of the weak: An L-tert-leucine-derived amine-thiourea catalyst (see scheme, green box) promotes the asymmetric vinylogous conjugate addition reaction between γ-aryl- and alkyl-substituted butenolides with the butenamides and enoates shown. Computational studies show the preference for the observed stereochemistry is a result of favourable weak non-bonding interactions, which stabilize the transition state. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Highly enantio- and diastereoselective reactions of γ-substituted butenolides through direct vinylogous conjugate additions

    KAUST Repository

    Zhang, Wen

    2012-09-05

    The strength of the weak: An L-tert-leucine-derived amine-thiourea catalyst (see scheme, green box) promotes the asymmetric vinylogous conjugate addition reaction between γ-aryl- and alkyl-substituted butenolides with the butenamides and enoates shown. Computational studies show the preference for the observed stereochemistry is a result of favourable weak non-bonding interactions, which stabilize the transition state. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Synthesis of 2,5-Disubstituted Octahydroquinolin-4-ones via anIntramolecular Hetero Diels-Alder Reaction

    Directory of Open Access Journals (Sweden)

    J. Antonio Palenzuela

    2007-02-01

    Full Text Available A route for the preparation of 2,5-disubstituted octahydroquinolin-4-ones, synthetic precursors of the decahydroquinoline-type toxins, is presented. The key steps are an asymmetric epoxidation and an intramolecular hetero Diels-Alder reaction between an activated diene and an imine. The presence of an allylic stereogenic center induces some selectivity and thus only two cycloadducts are obtained in 70:30 ratio and good yield.

  19. Porous asymmetric SiO2-g-PMMA nanoparticles produced by phase inversion

    KAUST Repository

    Munirasu, Selvaraj

    2014-07-22

    A new kind of asymmetric organic-inorganic porous structure has been proposed. Asymmetric lattices of polymer grafted silica nanoparticles were manufactured by casting and phase inversion in water. Silica nanoparticles were first functionalized with 3-(dimethylethoxysilyl)propyl-2-bromoisobutyrate, followed by grafting of poly(methylmethacrylate) (PMMA) segments, performed by atom-transfer radical polymerization. Mechanically stable self-standing films were prepared by casting a dispersion of functionalized nanoparticles in different solvents and immersion in water. The resulting asymmetrically porous morphology and nanoparticle assembly was characterized by scanning electron and atomic force microscopy. The PMMA functionalized SiO2 hybrid material in acetone or acetone/dioxane led to the best-assembled structures. Porous asymmetric membranes were prepared by adding free PMMA and PMMA terminated with hydrophilic hydroxyl group. Nitrogen flow of 2800 L m-2 h -1 was measured at 1.3 bar demonstrating the porosity and potential application for membrane technology. © 2014 Springer Science+Business Media New York.

  20. An ylide transformation of rhodium(I) carbene: enantioselective three-component reaction through trapping of rhodium(I)-associated ammonium ylides by β-nitroacrylates.

    Science.gov (United States)

    Ma, Xiaochu; Jiang, Jun; Lv, Siying; Yao, Wenfeng; Yang, Yang; Liu, Shunying; Xia, Fei; Hu, Wenhao

    2014-11-24

    The chiral Rh(I)-diene-catalyzed asymmetric three-component reaction of aryldiazoacetates, aromatic amines, and β-nitroacrylates was achieved to obtain γ-nitro-α-amino-succinates in good yields and with high diastereo- and enantioselectivity. This reaction is proposed to proceed through the enantioselective trapping of Rh(I)-associated ammonium ylides by nitroacrylates. This new transformation represents the first example of Rh(I)-carbene-induced ylide transformation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.