Sample records for scaleable catalytic asymmetric

  1. Catalytic asymmetric fluorinations. (United States)

    Bobbio, Carla; Gouverneur, Véronique


    The appearance of structurally diverse fluorinating reagents displaying a large spectrum of reactivity has been critical to the development of the catalytic asymmetric fluorination processes known to date. In this article, we discuss how this area of research emerged and which strategies have allowed for the successful development of both nucleophilic and electrophilic catalytic enantioselective fluorinations. We also present the fundamental understanding of catalytic activity and enantioselectivity for the most efficient processes and highlight the first synthetic application with the preparation of a complex fluorinated target.

  2. Catalytic Asymmetric Synthesis of Phosphine Boronates. (United States)

    Hornillos, Valentín; Vila, Carlos; Otten, Edwin; Feringa, Ben L


    The first catalytic enantioselective synthesis of ambiphilic phosphine boronate esters is presented. The asymmetric boration of α,β-unsaturated phosphine oxides catalyzed by a copper bisphosphine complex affords optically active organoboronate esters that bear a vicinal phosphine oxide group in good yields and high enantiomeric excess. The synthetic utility of the products is demonstrated through stereospecific transformations into multifunctional optically active compounds. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Catalytic Asymmetric Synthesis of Butenolides and Butyrolactones. (United States)

    Mao, Bin; Fañanás-Mastral, Martín; Feringa, Ben L


    γ-Butenolides, γ-butyrolactones, and derivatives, especially in enantiomerically pure form, constitute the structural core of numerous natural products which display an impressive range of biological activities which are important for the development of novel physiological and therapeutic agents. Furthermore, optically active γ-butenolides and γ-butyrolactones serve also as a prominent class of chiral building blocks for the synthesis of diverse biological active compounds and complex molecules. Taking into account the varying biological activity profiles and wide-ranging structural diversity of the optically active γ-butenolide or γ-butyrolactone structure, the development of asymmetric synthetic strategies for assembling such challenging scaffolds has attracted major attention from synthetic chemists in the past decade. This review offers an overview of the different enantioselective synthesis of γ-butenolides and γ-butyrolactones which employ catalytic amounts of metal complexes or organocatalysts, with emphasis focused on the mechanistic issues that account for the observed stereocontrol of the representative reactions, as well as practical applications and synthetic potentials.

  4. Catalytic asymmetric alkylation of ketones using organometallic reagents

    NARCIS (Netherlands)

    Madduri, Ashoka V.R.; Harutyunyan, Syuzanna R.; Minnaard, Adriaan J.


    The catalytic asymmetric synthesis of tertiary alcohols by the addition of organometallic reagents to ketones is of central importance in organic chemistry. The resulting quaternary stereocentres are difficult to prepare selectively by other means despite their widespread occurrence in natural

  5. Catalytic Asymmetric Addition Reaction of Dialkylzinc to Nitrone Utilizing Tartaric Acid Ester as a Chiral Auxiliary

    National Research Council Canada - National Science Library

    Ukaji, Yutaka; Shimizu, Yuuko; Kenmoku, Yuuichi; Ahmed, Alauddin; Inomata, Katsuhiko


    The catalytic asymmetric addition reaction of dialkylzinc to carbon-nitrogen double bond in 3,4-dihydroisoquinoline N-oxide derivatives was achieved by utilizing a catalytic amount of dicyclopentyl (R,R...

  6. Scaleable Clean Aluminum Melting Systems

    Energy Technology Data Exchange (ETDEWEB)

    Han, Q.; Das, S.K. (Secat, Inc.)


    The project entitled 'Scaleable Clean Aluminum Melting Systems' was a Cooperative Research and Development Agreements (CRADAs) between Oak Ridge National Laboratory (ORNL) and Secat Inc. The three-year project was initially funded for the first year and was then canceled due to funding cuts at the DOE headquarters. The limited funds allowed the research team to visit industrial sites and investigate the status of using immersion heaters for aluminum melting applications. Primary concepts were proposed on the design of furnaces using immersion heaters for melting. The proposed project can continue if the funding agency resumes the funds to this research. The objective of this project was to develop and demonstrate integrated, retrofitable technologies for clean melting systems for aluminum in both the Metal Casting and integrated aluminum processing industries. The scope focused on immersion heating coupled with metal circulation systems that provide significant opportunity for energy savings as well as reduction of melt loss in the form of dross. The project aimed at the development and integration of technologies that would enable significant reduction in the energy consumption and environmental impacts of melting aluminum through substitution of immersion heating for the conventional radiant burner methods used in reverberatory furnaces. Specifically, the program would couple heater improvements with furnace modeling that would enable cost-effective retrofits to a range of existing furnace sizes, reducing the economic barrier to application.

  7. Water-accelerated tandem Claisen rearrangement-catalytic asymmetric carboalumination. (United States)

    Wipf, P; Ribe, S


    [reaction: see text] The addition of stoichiometric quantities of water accelerates both the trimethylaluminum-mediated aromatic Claisen reaction and the chiral zirconocene-catalyzed asymmetric carboalumination of terminal alkenes. The two reactions occur in a tandem sequence resulting in the selective formation of two new C-C and one C-O bond after oxidative quench of the intermediate trialkylalane.

  8. Catalytic Asymmetric Synthesis of Dihydrofurans and Cyclopentenols with Tertiary Stereocenters

    NARCIS (Netherlands)

    Wu, Zhongtao; Madduri, Ashoka V.R.; Harutyunyan, Syuzanna R.; Minnaard, Adriaan J.

    A new asymmetric synthesis of dihydrofurans and cyclopentenols has been developed and is based on the copper-catalyzed 1,2-addition of Grignard reagents to enones in combination with Sonogashira coupling/cyclization or ring-closing metathesis. By this approach, dihydrofurans with an

  9. A Catalytic, Asymmetric Formal Synthesis of (+)-Hamigeran B

    KAUST Repository

    Mukherjee, Herschel


    A concise asymmetric, formal synthesis of (+)-hamigeran B is reported. A Pd-catalyzed, decarboxylative allylic alkylation, employing a trifluoromethylated derivative of t-BuPHOX, is utilized as the enantioselective step to form the critical quaternary carbon center in excellent yield and enantioselectivity. The product is converted in three steps to a late-stage intermediate previously used in the synthesis of hamigeran B.

  10. Concise enantioselective synthesis of duloxetine via direct catalytic asymmetric aldol reaction of thioamide. (United States)

    Suzuki, Yuta; Iwata, Mitsutaka; Yazaki, Ryo; Kumagai, Naoya; Shibasaki, Masakatsu


    Direct catalytic asymmetric aldol reaction of thioamide offers a new entry to the concise enantioselective synthesis of duloxetine. The direct aldol protocol was scalable (>20 g) to afford the aldol product in 92% ee after LiAlH(4) reduction, and 84% of the chiral ligand was recovered after recrystallization. The following four steps of transformation delivered duloxetine.

  11. Catalytic asymmetric aza-Darzens reaction with a vaulted biphenanthrol magnesium phosphate salt. (United States)

    Larson, Shawn E; Li, Guilong; Rowland, Gerald B; Junge, Denise; Huang, Rongcai; Woodcock, H Lee; Antilla, Jon C


    Conditions for a catalytic asymmetric aza-Darzens aziridine synthesis mediated by a vaulted biphenanthrol (VAPOL) magnesium phosphate salt is described. Using simple substrates, this methodology explores the scope and reactivity of a new magnesium catalyst for an aziridination reaction capable of building chirality and complexity simultaneously.

  12. Catalytic asymmetric synthesis of enantiopure isoprenoid building blocks : application in the synthesis of apple leafminer pheromones

    NARCIS (Netherlands)

    van Summeren, RP; Reijmer, SJW; Feringa, BL; Minnaard, AJ


    The first catalytic asymmetric procedure capable of preparing all 4 diastereoisomers (ee > 99%, de > 98%) of a versatile saturated isoprenoid building block was developed and the value of this new method was demonstrated in its application to the concise total synthesis of two pheromones.

  13. Catalytic Asymmetric Transfer Hydrogenation of Imines: Recent Advances. (United States)

    Foubelo, Francisco; Yus, Miguel


    In this review article recent developments in the asymmetric transfer hydrogenation of imines from 2008 up to today are presented. The main methodology involves either metal-catalyzed procedures in the presence of a chiral ligand or organocatalyzed technologies using a Hantzsch ester and a chiral BINOL-derived phosphoric acid. The most important procedures are collected, paying special attention to the application of this methodology in synthetic organic chemistry. Copyright © 2015 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. A One-Pot Tandem Strategy in Catalytic Asymmetric Vinylogous Aldol Reaction of Homoallylic Alcohols. (United States)

    Hou, Xufeng; Jing, Zhenzhong; Bai, Xiangbin; Jiang, Zhiyong


    Reported is a rationally-designed one-pot sequential strategy that allows homoallylic alcohols to be employed in a catalytic, asymmetric, direct vinylogous aldol reaction with a series of activated acyclic ketones, including trifluoromethyl ketones, γ-ketoesters, and α-keto phosphonates, in high yields (up to 95%) with excellent regio- and enantio-selectivity (up to 99% ee). This modular combination, including Jones oxidation and asymmetric organocatalysis, has satisfactory compatibility and reliability even at a 20 mmol scale, albeit without intermediary purification.

  15. Catalytic asymmetric generation of (Z)-disubstituted allylic alcohols. (United States)

    Salvi, Luca; Jeon, Sang-Jin; Fisher, Ethan L; Carroll, Patrick J; Walsh, Patrick J


    A one-pot method for the direct preparation of enantioenriched (Z)-disubstituted allylic alcohols is introduced. Hydroboration of 1-halo-1-alkynes with dicyclohexylborane, reaction with t-BuLi, and transmetalation with dialkylzinc reagents generate (Z)-disubstituted vinylzinc intermediates. In situ reaction of these reagents with aldehydes in the presence of a catalyst derived from (-)-MIB generates (Z)-disubstituted allylic alcohols. It was found that the resulting allylic alcohols were racemic, most likely due to a rapid addition reaction promoted by LiX (X = Br and Cl). To suppress the LiX-promoted reaction, a series of inhibitors were screened. It was found that 20-30 mol % tetraethylethylenediamine inhibited LiCl without inhibiting the chiral zinc-based Lewis acid. In this fashion, (Z)-disubstituted allylic alcohols were obtained with up to 98% ee. The asymmetric (Z)-vinylation could be coupled with tandem diastereoselective epoxidation reactions to provide epoxy alcohols and allylic epoxy alcohols with up to three contiguous stereogenic centers, enabling the rapid construction of complex building blocks with high levels of enantio- and diastereoselectivity.

  16. Catalytic asymmetric carbon-carbon bond formation via allylic alkylations with organolithium compounds. (United States)

    Pérez, Manuel; Fañanás-Mastral, Martín; Bos, Pieter H; Rudolph, Alena; Harutyunyan, Syuzanna R; Feringa, Ben L


    Carbon-carbon bond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents. Remarkably, for extremely reactive organolithium compounds, which are among the most broadly used reagents in chemical synthesis, a general catalytic methodology for enantioselective C-C formation has proven elusive, until now. Here, we report a copper-based chiral catalytic system that allows carbon-carbon bond formation via allylic alkylation with alkyllithium reagents, with extremely high enantioselectivities and able to tolerate several functional groups. We have found that both the solvent used and the structure of the active chiral catalyst are the most critical factors in achieving successful asymmetric catalysis with alkyllithium reagents. The active form of the chiral catalyst has been identified through spectroscopic studies as a diphosphine copper monoalkyl species.

  17. Catalytic Asymmetric Inverse-Electron-Demand Hetero-Diels-Alder Reactions. (United States)

    Xie, Mingsheng; Lin, Lili; Feng, Xiaoming


    In this review, the recent developments in catalytic asymmetric inverse-electron-demand hetero-Diels-Alder reaction, which is recognized as one of the most powerful routes to construct highly functionalized and enantioenriched six-membered heterocycles, are described. The article is organized on the basis of different kinds of electron-deficient heterodienes, including α,β-unsaturated ketones/aldehydes, o-benzoquinones, α,β-unsaturated imines, N-aryl imines, o-benzoqinone imides, and other aza-olefins. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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


    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.

  19. The effect of particle size and ligand configuration on the asymmetric catalytic properties of proline-functionalized Pt-nanoparticles

    DEFF Research Database (Denmark)

    Schrader, Imke; Neumann, Sarah; Himstedt, Rieke


    The effect of particle size on the asymmetric catalytic properties of supported ligand-functionalized nanoparticles (NPs) was investigated for the first time and found to alter significantly the activity but surprisingly not the stereoselectivity. These results suggest that the stereoselectivity...... of these complex systems is primarily determined by the ligand-reactant interaction, whereas the activity is determined by the particle size....

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

    KAUST Repository

    Hong, Allen Y.


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Yong Chul; Ahn, Dae Jun; Lee, Woo Sun; Lee, Seung Han; Ahn, Kwang Hyun [Chonnam National University, Gwangju (Korea, Republic of)


    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.

  2. 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.


    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

  3. Development of atom-economical catalytic asymmetric reactions under proton transfer conditions: construction of tetrasubstituted stereogenic centers and their application to therapeutics. (United States)

    Kumagai, Naoya


    The development of atom-economical catalytic asymmetric reactions based on two distinct sets of catalyst, a rare earth metal/amide-based ligand catalyst and a soft Lewis acid/hard Brønsted base catalyst, is reviewed. These catalytic systems exhibit high catalytic activity and stereoselectivity by harnessing a cooperative catalysis through hydrogen bond/metal coordination and soft-soft interactions/hard-hard interactions, respectively. The effectiveness of these cooperative catalysts is clearly delineated by the high stereoselectivity in reactions with highly coordinative substrates, and the specific activation of otherwise low-reactive pronucleophiles under proton transfer conditions. The rare earth metal/amide-based ligand catalyst was successfully applied to catalytic asymmetric aminations, nitroaldol (Henry) reactions, Mannich-type reactions, and conjugate addition reactions, generating stereogenic tetrasubstituted centers. Catalytic asymmetric amination and anti-selective catalytic asymmetric nitroaldol reactions were successfully applied to the efficient enantioselective synthesis of therapeutic candidates, such as AS-3201 and the β(3)-adrenoreceptor agonist, showcasing the practical utility of the present protocols. The soft Lewis acid/hard Brønsted base cooperative catalyst was specifically developed for the chemoselective activation of soft Lewis basic allylic cyanides and thioamides, which are otherwise low-reactive pronucleophiles. The cooperative action of the catalyst allowed for efficient catalytic generation of active carbon nucleophiles in situ, which were integrated into subsequent enantioselective additions to carbonyl-type electrophiles.

  4. Exploring the Catalytic Promiscuity of Phenolic Acid Decarboxylases: Asymmetric, 1,6-Conjugate Addition of Nucleophiles Across 4-Hydroxystyrene. (United States)

    Payer, Stefan E; Sheng, Xiang; Pollak, Hannah; Wuensch, Christiane; Steinkellner, Georg; Himo, Fahmi; Glueck, Silvia M; Faber, Kurt


    The catalytic promiscuity of a ferulic acid decarboxylase from Enterobacter sp. (FDC_ E s) and phenolic acid decarboxylases (PADs) for the asymmetric conjugate addition of water across the C=C bond of hydroxystyrenes was extended to the N-, C- and S-nucleophiles methoxyamine, cyanide and propanethiol to furnish the corresponding addition products in up to 91% ee . The products obtained from the biotransformation employing the most suitable enzyme/nucleophile pairs were isolated and characterized after optimizing the reaction conditions. Finally, a mechanistic rationale supported by quantum mechanical calculations for the highly ( S )-selective addition of cyanide is proposed.

  5. New biphenol-based, fine-tunable monodentate phosphoramidite ligands for catalytic asymmetric transformations. (United States)

    Hua, Zihao; Vassar, Victor C; Choi, Hojae; Ojima, Iwao


    Monodentate phosphoramidite ligands have been developed based on enantiopure 6,6'-dimethylbiphenols with axial chirality. These chiral ligands are easy to prepare and flexible for modifications. The fine-tuning capability of these ligands plays a significant role in achieving high enantioselectivity in the asymmetric hydroformylation of allyl cyanide and the conjugate addition of diethylzinc to cycloalkenones.

  6. New biphenol-based, fine-tunable monodentate phosphoramidite ligands for catalytic asymmetric transformations


    Hua, Zihao; Vassar, Victor C.; Choi, Hojae; OJIMA, IWAO


    Monodentate phosphoramidite ligands have been developed based on enantiopure 6,6′-dimethylbiphenols with axial chirality. These chiral ligands are easy to prepare and flexible for modifications. The fine-tuning capability of these ligands plays a significant role in achieving high enantioselectivity in the asymmetric hydroformylation of allyl cyanide and the conjugate addition of diethylzinc to cycloalkenones.

  7. Catalytic asymmetric carbon-carbon bond formation via allylic alkylations with organolithium compounds

    NARCIS (Netherlands)

    Perez, Manuel; Fananas Mastral, Martin; Bos, Pieter H.; Rudolph, Alena; Harutyunyan, Syuzanna R.; Feringa, Ben L.

    Carbon-carbon bond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents.

  8. Catalytic Asymmetric [4 + 1] Annulation of Sulfur Ylides with Copper-Allenylidene Intermediates. (United States)

    Wang, Qiang; Li, Tian-Ren; Lu, Liang-Qiu; Li, Miao-Miao; Zhang, Kai; Xiao, Wen-Jing


    The first copper-catalyzed asymmetric decarboxylative [4 + 1] cycloaddition of propargylic carbamates and sulfur ylides was successfully developed. This strategy led to a series of chiral indolines with synthetically flexible alkyne groups in good yields and with high enantio- and diastereoselectivities (up to 99% yield, 98% ee, and >95:5 dr). A possible mechanism and stereoinduction mode with copper-allenylidenes were proposed as the possible dipolar intermediate.

  9. Catalytic asymmetric 1,4-addition reactions using alpha,beta-unsaturated N-acylpyrroles as highly reactive monodentate alpha,beta-unsaturated ester surrogates. (United States)

    Matsunaga, Shigeki; Kinoshita, Tomofumi; Okada, Shigemitsu; Harada, Shinji; Shibasaki, Masakatsu


    Synthesis and application of alpha,beta-unsaturated N-acylpyrroles as highly reactive, monodentate ester surrogates in the catalytic asymmetric epoxidation and Michael reactions are described. alpha,beta-Unsaturated N-acylpyrroles with various functional groups were synthesized by the Wittig reaction using ylide 2. A Sm(O-i-Pr)(3)/H(8)-BINOL complex was the most effective catalyst for the epoxidation to afford pyrrolyl epoxides in up to 100% yield and >99% ee. Catalyst loading was successfully reduced to as little as 0.02 mol % (substrate/catalyst = 5000). The high turnover frequency and high volumetric productivity of the present reaction are also noteworthy. In addition, a sequential Wittig olefination-catalytic asymmetric epoxidation reaction was developed, providing efficient one-pot access to optically active epoxides from various aldehydes in high yield and ee (96-->99%). In a direct catalytic asymmetric Michael reaction of hydroxyketone promoted by the Et(2)Zn/linked-BINOL complex, Michael adducts were obtained in good yield (74-97%), dr (69/31-95/5), and ee (73-95%). This represents the first direct catalytic asymmetric Michael reaction of unmodified ketone to an alpha,beta-unsaturated carboxylic acid derivative. The properties of alpha,beta-unsaturated N-acylpyrrole are also discussed. Finally, the utility of the N-acylpyrrole unit for further transformations is demonstrated.

  10. One-Step Homologation for the Catalytic Asymmetric Synthesis of Deoxypropionates. (United States)

    Xu, Shiqing; Li, Haijun; Komiyama, Masato; Oda, Akimichi; Negishi, Ei-Ichi


    A one-step homologation protocol for the synthesis of natural products containing deoxypropionate motif is described by the combination of Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)-Pd-catalyzed vinylation and ZACA-oxidation reaction. In contrast to most other synthetic strategies used to date that typically require three steps per deoxypropionate unit due to the functional-group interconversions, our one-step homologation strategy promises to provide a general and more efficient synthetic route toward deoxypropionate natural products as exemplified by significant improvements in the syntheses of intermediates and/or final products of mycolipenic acid 1 and its analogue 2, (-)-rasfonin, and syn- and anti-dicarboxylic acids 5 and 6. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Asymmetric catalysis at a distance: catalytic, site-selective phosphorylation of teicoplanin. (United States)

    Han, Sunkyu; Miller, Scott J


    We report three distinct, peptide-based catalysts that enable site-selective phosphorylation of three distinct hydroxyl groups within the complex glycopeptide antibiotic teicoplanin A2-2. Two of the catalysts are based on a design that capitalizes on a catalyst-substrate interaction that mimics the biological mechanism of action for teicoplanin. These catalysts are based on a DXaa-DXaa peptide motif that is known to target the teicoplanin structure in a specific manner. The third was identified through evaluation of a set of catalysts that had been developed for historically distinct projects. Each catalyst contains additional functionality designed to dispose a catalytic moiety (a nucleophilic alkylimidazole) at a different region of the glycopeptide structure. A combination of mass spectrometry and 2D-NMR spectroscopy allowed structural assignment of the distinct phosphorylated teicoplanin derivatives. Mechanistic studies are also reported that support the hypotheses that led to the discovery of the catalysts. In this manner, small molecule catalysts have been achieved that allow rational, catalytic control over reactions at sites that are separated by 11.6, 16.5, and nearly 17.7 Å, based on the X-ray crystal structure of teicoplanin A2-2. Finally, we report the biological activity of the new phosphorylated teicoplanin analogs and compare the results to the natural product itself.

  12. Catalytic asymmetric trifluoromethylthiolation via enantioselective [2,3]-sigmatropic rearrangement of sulfonium ylides (United States)

    Zhang, Zhikun; Sheng, Zhe; Yu, Weizhi; Wu, Guojiao; Zhang, Rui; Chu, Wen-Dao; Zhang, Yan; Wang, Jianbo


    The trifluoromethylthio (SCF3) functional group has been of increasing importance in drug design and development as a consequence of its unique electronic properties and high stability coupled with its high lipophilicity. As a result, methods to introduce this highly electronegative functional group have attracted considerable attention in recent years. Although significant progress has been made in the introduction of SCF3 functionality into a variety of molecules, there remain significant challenges regarding the enantioselective synthesis of SCF3-containing compounds. Here, an asymmetric trifluoromethylthiolation that proceeds through the enantioselective [2,3]-sigmatropic rearrangement of a sulfonium ylide generated from a metal carbene and sulfide (Doyle-Kirmse reaction) has been developed using chiral Rh(II) and Cu(I) catalysts. This transformation features mild reaction conditions and excellent enantioselectivities (up to 98% yield and 98% e.e.), thus providing a unique, highly efficient and enantioselective method for the construction of C(sp3)-SCF3 bonds bearing chiral centres.

  13. Biologically active Phytophthora mating hormone prepared by catalytic asymmetric total synthesis (United States)

    Harutyunyan, Syuzanna R.; Zhao, Zhijian; den Hartog, Tim; Bouwmeester, Klaas; Minnaard, Adriaan J.; Feringa, Ben L.; Govers, Francine


    A Phytophthora mating hormone with an array of 1,5-stereogenic centers has been synthesized by using our recently developed methodology of catalytic enantioselective conjugate addition of Grignard reagents. We applied this methodology in a diastereo- and enantioselective iterative route and obtained two of the 16 possible stereoisomers of Phytophthora hormone α1. These synthetic stereoisomers induced the formation of sexual spores (oospores) in A2 mating type strains of three heterothallic Phytophthora species, P. infestans, P. capsici, and P. nicotianae but not in A1 mating type strains. The response was concentration-dependent, and the oospores were viable. These results demonstrate that the biological activity of the synthetic hormone resembles that of the natural hormone α1. Mating hormones are essential components in the sexual life cycle of a variety of organisms. For plant pathogens like Phytophthora, sexual reproduction is important as a source of genetic variation. Moreover, the thick-walled oospores are the most durable propagules that can survive harsh environmental conditions. Sexual reproduction can thus greatly affect disease epidemics. The availability of synthetic compounds mimicking the activity of Phytophthora mating hormone will be instrumental for further unravelling sexual reproduction in this important group of plant pathogens. PMID:18559862

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

    KAUST Repository

    Cai, Yunfei


    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.

  15. Catalytic asymmetric access to alpha,beta unsaturated delta-lactones through a vinylogous aldol reaction: application to the total synthesis of the Prelog-Djerassi lactone. (United States)

    Bluet, G; Bazán-Tejeda, B; Campagne, J M


    [reaction--see text] A one-step catalytic asymmetric access to alpha,beta unsaturated delta-lactones is described, using a vinylogous Mukaiyama-aldol reaction between a gamma-substituted dienolate and various aldehydes in the presence of Carreira catalyst CuF.(S)-tolBinap. This methodology has been further applied to a straightforward access to the Prelog-Djerassi lactone.

  16. Catalytic asymmetric formation of delta-lactones from unsaturated acyl halides. (United States)

    Tiseni, Paolo S; Peters, René


    Previously unexplored enantiopure zwitterionic ammonium dienolates have been utilized in this work as reactive intermediates that act as diene components in hetero-Diels-Alder reactions (HDAs) with aldehydes to produce optically active delta-lactones, subunits of numerous bioactive products. The dienolates were generated in situ from E/Z mixtures of alpha,beta-unsaturated acid chlorides by use of a nucleophilic quinidine derivative and Sn(OTf)(2) as co-catalyst. The latter component was not directly involved in the cycloaddition step with aldehydes and simply facilitated the formation of the reactive dienolate species. The scope of the cycloaddition was considerably improved by use of a complex formed from Er(OTf)(3) and a simple commercially available norephedrine-derived ligand that tolerated a broad range of aromatic and heteroaromatic aldehydes for a cooperative bifunctional Lewis-acid-/Lewis-base-catalyzed reaction, providing alpha,beta-unsaturated delta-lactones with excellent enantioselectivities. Mechanistic studies confirmed the formation of the dienolate intermediates for both catalytic systems. The active Er(III) complex is most likely a monomeric species. Interestingly, all lanthanides can catalyze the title reaction, but the efficiency in terms of yield and enantioselectivity depends directly on the radius of the Ln(III) ion. Similarly, use of the pseudolanthanides Sc(III) and Y(III) also resulted in product formation, whereas the larger La(III) and other transition metal salts, as well as main group metal salts, proved to be inefficient. In addition, various synthetic transformations of 6-CCl(3)- or 4-silyl-substituted alpha,beta-unsaturated delta-lactones, giving access to a number of valuable delta-lactone building blocks, were investigated.

  17. Catalytic

    Directory of Open Access Journals (Sweden)

    S.A. Hanafi


    Full Text Available A series of dealuminated Y-zeolites impregnated by 0.5 wt% Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt% were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N2 physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydroconversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 °C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption–desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2–4 nm and 7–8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5Pt–0.3Cr/D18H–Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5Pt–0.6Ni/D18H–Y catalyst can be designed as most suitable as a cracking catalyst.

  18. 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

  19. Structure Investigation of Ti(IV)BODOLates Involved in the Catalytic Asymmetric Reduction of Ketones Using Catecholborane

    DEFF Research Database (Denmark)

    Sarvary, Ian; Norrby, Per-Ola; Frejd, Torbjörn


    The complexes formed on mixing Ti(OiPr)4 and bicyclo-octanediols (BODOLs) 1 and 2 (1:1) are useful as chiral catalysts in asymmetric reductions and were investigated by 1HNMR-spectroscopy and by computational methods. A consistent picture emerged of head-to-tail dimers being kept together via a T......-O-Ti-O m-oxo bridge similar to the Ti-tartrates but different from the corresponding Ti-BINOLates and the Ti-TADDOLates....

  20. Total syntheses of (–)-Borrelidin and (–)-Doliculide and the development of the catalytic asymmetric addition of Grignard reagents to ketones

    NARCIS (Netherlands)

    Madduri Venkata, Ashoka Vardhan Reddy


    This thesis describes the application of copper-catalyzed asymmetric conjugate addition and ruthenium-catalyzed asymmetric hydrogenation in novel total syntheses of the macrocyclic polyketides Borrelidin and Doliculide. A second topic in the thesis comprizes the development of a novel asymmetric

  1. A novel asymmetric di-Ni(II) system as a highly efficient functional model for phosphodiesterase: synthesis, structures, physicochemical properties and catalytic kinetics. (United States)

    Ren, Yan-wei; Lu, Jia-xian; Cai, Bo-wei; Shi, Da-bin; Jiang, Huan-feng; Chen, Jun; Zheng, De; Liu, Bin


    A novel asymmetric phenol-based 'end-off' dinucleating ligand 2-{[(2-piperidylmethyl)amino]methyl}-4-bromo-6-[(1-methylhomopiperazine-4-yl)methyl]phenol (HL) and three dinuclear nickel(II) complexes, [Ni₂L(μ-OH)] (ClO₄)₂ (1), [Ni₂L(DNBA)₂(CH₃CN)₂]BPh₄ (2) and [Ni₂L(BPP)₂(CH₃CN)₂]BPh₄ (3) have been synthesized and characterized by a variety of techniques including: NMR, infrared and UV-vis spectroscopies, mass spectrometry, elemental analysis, molar conductivity, thermal analysis, magnetochemistry and single-crystal X-ray diffractometry. The UV-vis spectrum of complex 1 exhibits a strong peak at 510 nm, a characteristic absorption of a d-d transition of the square-planar four-coordinated Ni(II) center. Utilizing this feature, the stepwise formation of mono- and dinickel centers in solution can be monitored. Phosphodiesterase activity of a dinuclear Ni(II) system (complex 1), formed in situ by a 2 : 1 mixture of Ni(2+) ions and the ligand HL, was investigated using bis(4-nitrophenyl)phosphate (BNPP) as the substrate. The pH dependence of the BNPP cleavage in water-ethanol (1 : 1, v/v) reveals a bell-shaped pH-k(obs) profile with an optimum at about pH 8.3 which is parallel to the formation of the dinuclear species [Ni₂L(μ-OH)](2+), according to the increase of the peak at 510 nm in the UV-vis absorption spectrum . These studies reveal that the di-Ni(II) system shows the highest catalytic activity reported so far, with an acceleration rate 1.28 × 10⁷ times faster than the uncatalyzed reaction. The bridging hydroxyl group in [Ni₂L(μ-OH)](2+) is responsible for the hydrolysis reaction. The possible mechanism for the BNPP cleavage promoted by di-Ni(II) system is proposed on the basis of kinetic and spectral analyses. This study provides a less common example of the asymmetric phosphodiesterase model, which is like the active sites of most native metallohydrolases.

  2. Multicatalyst system in asymmetric catalysis

    CERN Document Server

    Zhou, Jian


    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

  3. Asymmetric Ion-Pairing Catalysis (United States)

    Brak, Katrien


    Charged intermediates and reagents are ubiquitous in organic transformations. The interaction of these ionic species with chiral neutral, anionic, or cationic small molecules has emerged as a powerful strategy for catalytic, enantioselective synthesis. This review describes developments in the burgeoning field of asymmetric ion-pairing catalysis with an emphasis on the insights that have been gleaned into the structural and mechanistic features that contribute to high asymmetric induction. PMID:23192886

  4. Asymmetric total synthesis of Apocynaceae hydrocarbazole alkaloids (+)-deethylibophyllidine and (+)-limaspermidine. (United States)

    Du, Ji-Yuan; Zeng, Chao; Han, Xiao-Jie; Qu, Hu; Zhao, Xian-He; An, Xian-Tao; Fan, Chun-An


    An unprecedented asymmetric catalytic tandem aminolysis/aza-Michael addition reaction of spirocyclic para-dienoneimides has been designed and developed through organocatalytic enantioselective desymmetrization. A unified strategy based on this key tandem methodology has been divergently explored for the asymmetric total synthesis of two natural Apocynaceae alkaloids, (+)-deethylibophyllidine and (+)-limaspermidine. The present studies not only enrich the tandem reaction design concerning the asymmetric catalytic assembly of a chiral all-carbon quaternary stereocenter contained in the densely functionalized hydrocarbazole synthons but also manifest the potential for the application of the asymmetric catalysis based on the para-dienone chemistry in asymmetric synthesis of natural products.

  5. (TIQ) Thiazole and Oxazoline Ligands for Asymmetric Henry Reactions

    African Journals Online (AJOL)


    TIQ) backbone were synthesized. Their application in the catalytic asymmetric Henry reaction was investigated with comparison to a corresponding TIQ oxazoline ligand. The Cu(II)-oxazoline complex was more reactive and furnished moderate ...

  6. The catalystic asymmetric synthesis of optically active epoxy ketones

    NARCIS (Netherlands)

    Marsman, Bertha Gerda


    In this thesis the use of catalytic asymmetric synthesis to prepare optically active epoxy ketones is described. This means that the auxiliary chirality, necessary to obtain an optically active product, is added in a catalytic quantity . In principle this is a very efficient way to make opticlly

  7. Catalytic Hydrogenation of Bio-Oil for Chemicals and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, Douglas C.


    The scope of work includes optimizing processing conditions and demonstrating catalyst lifetime for catalyst formulations that are readily scaleable to commercial operations. We use a bench-scale, continuous-flow, packed-bed, catalytic, tubular reactor, which can be operated in the range of 100-400 mL/hr., from 50-400 C and up to 20MPa (see Figure 1). With this unit we produce upgraded bio-oil from whole bio-oil or useful bio-oil fractions, specifically pyrolytic lignin. The product oils are fractionated, for example by distillation, for recovery of chemical product streams. Other products from our tests have been used in further testing in petroleum refining technology at UOP and fractionation for product recovery in our own lab. Further scale-up of the technology is envisioned and we will carry out or support process design efforts with industrial partners, such as UOP.

  8. Asymmetric fluorocyclizations of alkenes. (United States)

    Wolstenhulme, Jamie R; Gouverneur, Véronique


    .g., TRIP and derivatives) brings into solution the resulting chiral Selectfluor reagent, now capable of asymmetric fluorocyclization. This strategy is best applied to a subset of substrates bearing a nucleophilic pendent group (benzamide is best) capable of hydrogen bonding for association with the chiral phosphate catalyst. These contributions focused on fluoroheterocyclization involving either O- or N-nucleophiles. As for other halocyclizations, alkenes armed with π C-nucleophiles represent the most demanding class of substrates for asymmetric F(+)-induced electrophilic fluorination-cyclization. Successful implementation required the design of new chiral Selectfluor reagents featuring stereogenicity on the DABCO core. These reagents, accessible from chiral vicinal diamines, allowed the synthesis of unusual chiral fluorine-containing tetracyclic compounds, some composed of carbon, hydrogen, and fluorine exclusively. The challenges associated with F(+)-induced fluorocarbocyclizations prompted methodologists to consider chemistry where the Csp(3)-F bond formation event follows a catalyst-controlled cyclization. An exciting development built on in the area of transition metal π-cyclization of polyenes leading to cationic metal-alkyl intermediates. When intercepted by oxidative fluorodemetalation with a F(+) source, the resulting products are complex polycyclic structures emerging from an overall catalytic cascade fluorocarbocyclization. Complementing F(+)-based reactions, examples of fluorocyclizations with fluoride in the presence of an oxidant were reported. Despite some exciting developments, the field of asymmetric fluorocyclizations is in its infancy and undoubtedly requires new activation modes, catalysts, as well as F(+) and F(-) reagents to progress into general retrosynthetic approach toward enantioenriched fluorocycles. Numerous opportunities emerge, not least the use of a latent fluorine source as a means to minimize background fluorination.

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

    DEFF Research Database (Denmark)

    Johannsen, Mogens; Yao, Sulan; Graven, Anette


    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- and enantiose......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...

  10. Asymmetric Ashes (United States)


    that oscillate in certain directions. Reflection or scattering of light favours certain orientations of the electric and magnetic fields over others. This is why polarising sunglasses can filter out the glint of sunlight reflected off a pond. When light scatters through the expanding debris of a supernova, it retains information about the orientation of the scattering layers. If the supernova is spherically symmetric, all orientations will be present equally and will average out, so there will be no net polarisation. If, however, the gas shell is not round, a slight net polarisation will be imprinted on the light. This is what broad-band polarimetry can accomplish. If additional spectral information is available ('spectro-polarimetry'), one can determine whether the asymmetry is in the continuum light or in some spectral lines. In the case of the Type Ia supernovae, the astronomers found that the continuum polarisation is very small so that the overall shape of the explosion is crudely spherical. But the much larger polarization in strongly blue-shifted spectral lines evidences the presence, in the outer regions, of fast moving clumps with peculiar chemical composition. "Our study reveals that explosions of Type Ia supernovae are really three-dimensional phenomena," says Dietrich Baade. "The outer regions of the blast cloud is asymmetric, with different materials found in 'clumps', while the inner regions are smooth." "This study was possible because polarimetry could unfold its full strength thanks to the light-collecting power of the Very Large Telescope and the very precise calibration of the FORS instrument," he adds. The research team first spotted this asymmetry in 2003, as part of the same observational campaign (ESO PR 23/03 and ESO PR Photo 26/05). The new, more extensive results show that the degree of polarisation and, hence, the asphericity, correlates with the intrinsic brightness of the explosion. The brighter the supernova, the smoother, or less clumpy

  11. Catalytic enantioselective conjugate addition with Grignard reagents

    NARCIS (Netherlands)

    Lopez, Fernando; Minnaard, Adriaan J.; Feringa, Ben L.

    In this Account, recent advances in catalytic asymmetric conjugate addition of Grignard reagents are discussed. Synthetic methodology to perform highly enantioselective Cu-catalyzed conjugate addition of Grignard reagents to cyclic enones with ee's up to 96% was reported in 2004 from our

  12. Catalytic converter

    Energy Technology Data Exchange (ETDEWEB)

    Liber, B.


    A catalytic converter is provided which is economical to manufacture and is not readily poisoned by contaminants in a gas stream such as would be encountered in the operation of an internal combustion engine, whereby an improved life expectancy of the unit can be achieved. The converter of the invention comprises a sintered porous body including molybdenum or a molybdenum-containing compound or a molybdenum complex. A method of forming a catlytic converter unit comprises forming a slurry including molybdenum or a molybdenum compound, forming the slurry into a sintered body member, and hardening or curing the same to form a self-sustaining body member. A method for treating an exhaust gas using the above catalytic converter is also disclosed. A preferred embodiment for an internal combustion engine is described. Examples of different catalytic compositions are included. 13 figs.

  13. Asymmetric conjugate addition of alkylzirconium reagents to α,β-unsaturated lactones. (United States)

    Maciver, Eleanor E; Maksymowicz, Rebecca M; Wilkinson, Nancy; Roth, Philippe M C; Fletcher, Stephen P


    The asymmetric synthesis of β-substituted lactones by catalytic asymmetric conjugate addition of alkyl groups to α,β-unsaturated lactones is reported. The method uses alkylzirconium nucleophiles prepared in situ from alkenes and the Schwartz reagent. Enantioselective additions to 6- and 7-membered lactones proceed at rt, tolerate a wide variety of functional groups, and are readily scalable. The method was used in a formal asymmetric synthesis of mitsugashiwalactone.

  14. Catalytic devices

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ming; Zhang, Xiang


    This disclosure provides systems, methods, and apparatus related to catalytic devices. In one aspect, a device includes a substrate, an electrically insulating layer disposed on the substrate, a layer of material disposed on the electrically insulating layer, and a catalyst disposed on the layer of material. The substrate comprises an electrically conductive material. The substrate and the layer of material are electrically coupled to one another and configured to have a voltage applied across them.

  15. Asymmetric bipolar membrane: A tool to improve product purity

    NARCIS (Netherlands)

    Balster, J.H.; Sumbharaju, R.; Srikantharajah, S.; Punt, Ineke G.M.; Stamatialis, Dimitrios; Jordan, V.; Wessling, Matthias


    Bipolar membranes (BPMs) are catalytic membranes for electro-membrane processes splitting water into protons and hydroxyl ions. To improve selectivity and current efficiency of BPMs, we prepare new asymmetric BPMs with reduced salt leakages. The flux of salt ions across a BPM is determined by the

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

    NARCIS (Netherlands)

    Jong, Johannes Cornelis de


    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

  17. Asymmetric Divisions in Oogenesis. (United States)

    Bilinski, Szczepan M; Kubiak, Jacek Z; Kloc, Malgorzata

    In the majority of animals, the oocyte/egg is structurally, molecularly, and functionally asymmetric. Such asymmetry is a prerequisite for a flawless fertilization and faithful segregation of maternal determinants during subsequent embryonic development. The oocyte asymmetry develops during oogenesis and must be maintained during consecutive and obligatorily asymmetric oogonial divisions, which depending on the species lead to the formation of either oocyte alone or oocyte and nurse cell complex. In the following chapter, we summarize current knowledge on the asymmetric oogonial divisions in invertebrate (insects) and vertebrate (Xenopus) species.

  18. Chiral Diamine-catalyzed Asymmetric Aldol Reaction

    Institute of Scientific and Technical Information of China (English)

    LI Hui; XU Da-zhen; WU Lu-lu; WANG Yong-mei


    A highly efficient catalytic system composed of a simple and commercially available chiral primary diamine (1R,2R)-cyclohexane-1,2-diamine(6) and trifluoroacetic acid(TFA) was employed for asymmetric Aldol reaction in i-PrOH at room temperature.A loading of 10%(molar fraction) catalyst 6 with TFA as a cocatalyst could catalyze the Aldol reactions of various ketones or aldehydes with a series of aromatic aldehydes,furnishing Aldol products in moderate to high yields(up to >99%) with enantioselectivities of up to >99% and diastereoselectivities of up to 99:1.

  19. Catalytic Asymmetric Generation of (Z)-Disubstituted Allylic Alcohols


    Salvi, Luca; Jeon, Sang-Jin; Fisher, Ethan L.; Carroll, Patrick J.; Walsh, Patrick J.


    A one-pot method for the direct preparation of enantioenriched (Z)-disubstituted allylic alcohols is introduced. Hydroboration of 1-halo-1-alkynes with dicyclohexylborane, reaction with t-BuLi, and transmetallation with dialkylzinc reagents generates (Z)-disubstituted vinylzinc intermediates. In situ reaction of these reagents with aldehydes in the presence of a catalyst derived from (−)-MIB generates (Z)-disubstituted allylic alcohols. It was found that the resulting allylic alcohols were ra...

  20. Catalytic asymmetric conjugate addition of Grignard reagents to chromones

    NARCIS (Netherlands)

    Vila, Carlos; Hornillos, Valentin; Fananas-Mastral, Martin; Feringa, Ben L.


    A highly regio- and enantioselective copper catalysed direct conjugate addition of Grignard reagents to chromones has been developed taking advantage of the reduced reactivity of the resulting magnesium enolates. This methodology tolerates a broad scope of alkyl Grignards including secondary alkyl

  1. Asymmetrical field emitter (United States)

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


    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.

  2. Asymmetrical international attitudes

    NARCIS (Netherlands)

    Van Oudenhoven, JP; Askevis-Leherpeux, F; Hannover, B; Jaarsma, R; Dardenne, B


    In general, attitudes towards nations have a fair amount of reciprocity: nations either like each other are relatively indifferent to each other or dislike each other Sometimes, however international attitudes are asymmetrical. In this study, we use social identity theory in order to explain

  3. 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.

  4. New mechanistic aspects of the asymmetric homogeneous hydrogenation of alkenes. (United States)

    Brown, J M; Giernoth, R


    Progress in homogeneous catalysis depends upon an understanding of the reaction mechanism; in asymmetric catalysis this entails an insight into the origins of enantioselectivity. Significant advances have been made in the area of alkene reduction catalyzed by rhodium or ruthenium complexes, which has been in tandem with the development of new, more effective ligands for the reaction. The combination of quantum chemical calculations and direct spectroscopic observation of catalytic intermediates has proved powerful in this regard.

  5. Highly asymmetric rice genomes

    Directory of Open Access Journals (Sweden)

    Chen Jian-Qun


    Full Text Available Abstract Background Individuals in the same species are assumed to share the same genomic set. However, it is not unusual to find an orthologous gene only in small subset of the species, and recent genomic studies suggest that structural rearrangements are very frequent between genomes in the same species. Two recently sequenced rice genomes Oryza sativa L. var. Nipponbare and O. sativa L. var. 93-11 provide an opportunity to systematically investigate the extent of the gene repertoire polymorphism, even though the genomic data of 93-11 derived from whole-short-gun sequencing is not yet as complete as that of Nipponbare. Results We compared gene contents and the genomic locations between two rice genomes. Our conservative estimates suggest that at least 10% of the genes in the genomes were either under presence/absence polymorphism (5.2% or asymmetrically located between genomes (4.7%. The proportion of these "asymmetric genes" varied largely among gene groups, in which disease resistance (R genes and the RLK kinase gene group had 11.6 and 7.8 times higher proportion of asymmetric genes than housekeeping genes (Myb and MADS. The significant difference in the proportion of asymmetric genes among gene groups suggests that natural selection is responsible for maintaining genomic asymmetry. On the other hand, the nucleotide diversity in 17 R genes under presence/absence polymorphism was generally low (average nucleotide diversity = 0.0051. Conclusion The genomic symmetry was disrupted by 10% of asymmetric genes, which could cause genetic variation through more unequal crossing over, because these genes had no allelic counterparts to pair and then they were free to pair with homologues at non-allelic loci, during meiosis in heterozygotes. It might be a consequence of diversifying selection that increased the structural divergence among genomes, and of purifying selection that decreased nucleotide divergence in each R gene locus.

  6. Chiral fullerenes from asymmetric catalysis. (United States)

    Maroto, Enrique E; Izquierdo, Marta; Reboredo, Silvia; Marco-Martínez, Juan; Filippone, Salvatore; Martín, Nazario


    Fullerenes are among the most studied molecules during the last three decades, and therefore, a huge number of chemical reactions have been tested on these new carbon allotropes. However, the aim of most of the reactions carried out on fullerenes has been to afford chemically modified fullerenes that are soluble in organic solvents or even water in the search for different mechanical, optical, or electronic properties. Therefore, although a lot of effort has been devoted to the chemical functionalization of these molecular allotropes of carbon, important aspects in the chemistry of fullerenes have not been properly addressed. In particular, the synthesis of chiral fullerenes at will in an efficient manner using asymmetric catalysis has not been previously addressed in fullerene science. Thus, despite the fact that the chirality of fullerenes has always been considered a fundamental issue, the lack of a general stereoselective synthetic methodology has restricted the use of enantiopure fullerene derivatives, which have usually been obtained only after highly expensive HPLC isolation on specific chiral columns or prepared from a pool of chiral starting materials. In this Account, we describe the first stereodivergent catalytic enantioselective syntheses in fullerene science, which have allowed the highly efficient synthesis of enantiomerically pure derivatives with total control of the stereochemical result using metallic catalysts and/or organocatalysts under very mild conditions. Density functional theory calculations strongly support the experimental findings for the assignment of the absolute configuration of the new stereocenters, which has also been ascertained by application of the sector rule and single-crystal X-ray diffraction. The use of the curved double bond of fullerene cages as a two-π-electron component in a variety of stereoselective cycloaddition reactions represents a challenging goal considering that, in contrast to most of the substituted

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


    Erli Sugiono; Magnus Rueping


    Summary A continuous-flow asymmetric organocatalytic photocyclization?transfer hydrogenation cascade reaction has been developed. The new protocol allows the synthesis of tetrahydroquinolines from readily available 2-aminochalcones using a combination of photochemistry and asymmetric Br?nsted 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 ...

  8. A combined continuous microflow photochemistry and asymmetric organocatalysis approach for the enantioselective synthesis of tetrahydroquinolines. (United States)

    Sugiono, Erli; Rueping, Magnus


    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.

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

    Directory of Open Access Journals (Sweden)

    Erli Sugiono


    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.

  10. Asymmetric catalysis at the mesoscale: gold nanoclusters embedded in chiral self-assembled monolayer as heterogeneous catalyst for asymmetric reactions. (United States)

    Gross, Elad; Liu, Jack H; Alayoglu, Selim; Marcus, Matthew A; Fakra, Sirine C; Toste, F Dean; Somorjai, Gabor A


    Research to develop highly versatile, chiral, heterogeneous catalysts for asymmetric organic transformations, without quenching the catalytic reactivity, has met with limited success. While chiral supramolecular structures, connected by weak bonds, are highly active for homogeneous asymmetric catalysis, their application in heterogeneous catalysis is rare. In this work, asymmetric catalyst was prepared by encapsulating metallic nanoclusters in chiral self-assembled monolayer (SAM), immobilized on mesoporous SiO2 support. Using olefin cyclopropanation as an example, it was demonstrated that by controlling the SAM properties, asymmetric reactions can be catalyzed by Au clusters embedded in chiral SAM. Up to 50% enantioselectivity with high diastereoselectivity were obtained while employing Au nanoclusters coated with SAM peptides as heterogeneous catalyst for the formation of cyclopropane-containing products. Spectroscopic measurements correlated the improved enantioselectivity with the formation of a hydrogen-bonding network in the chiral SAM. These results demonstrate the synergetic effect of the catalytically active metallic sites and the surrounding chiral SAM for the formation of a mesoscale enantioselective catalyst.

  11. Asymmetric extractions in orthodontics

    Directory of Open Access Journals (Sweden)

    Camilo Aquino Melgaço


    Full Text Available INTRODUCTION: Extraction decisions are extremely important in during treatment planning. In addition to the extraction decision orthodontists have to choose what tooth should be extracted for the best solution of the problem and the esthetic/functional benefit of the patient. OBJECTIVE: This article aims at reviewing the literature relating the advantages, disadvantages and clinical implications of asymmetric extractions to orthodontics. METHODS: Keywords were selected in English and Portuguese and the EndNote 9 program was used for data base search in PubMed, Web of Science (WSc and LILACS. The selected articles were case reports, original articles and prospective or retrospective case-control studies concerning asymmetrical extractions of permanent teeth for the treatment of malocclusions. CONCLUSION: According to the literature reviewed asymmetric extractions can make some specific treatment mechanics easier. Cases finished with first permanent molars in Class II or III relationship in one or both sides seem not to cause esthetic or functional problems. However, diagnosis knowledge and mechanics control are essential for treatment success.

  12. Asymmetric Evolutionary Games.

    Directory of Open Access Journals (Sweden)

    Alex McAvoy


    Full Text Available 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.

  13. Asymmetric Evolutionary Games. (United States)

    McAvoy, Alex; Hauert, Christoph


    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.

  14. Asymmetric synthesis v.4

    CERN Document Server

    Morrison, James


    Asymmetric Synthesis, Volume 4: The Chiral Carbon Pool and Chiral Sulfur, Nitrogen, Phosphorus, and Silicon Centers describes the practical methods of obtaining chiral fragments. Divided into five chapters, this book specifically examines initial chiral transmission and extension. The opening chapter describes the so-called chiral carbon pool, the readily available chiral carbon fragments used as building blocks in synthesis. This chapter also provides a list of 375 chiral building blocks, along with their commercial sources, approximate prices, and methods of synthesis. Schemes involving

  15. Asymmetric Organocatalytic Cycloadditions

    DEFF Research Database (Denmark)

    Mose, Rasmus


    were pioneered by Otto Paul Hermann Diels and Kurt Alder who discovered what later became known as the Diels Alder reaction. The Diels Alder reaction is a [4+2] cycloaddition in which a π4 component reacts with a π2 component via a cyclic transition state to generate a 6 membered ring. This reaction...... 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...

  16. Asymmetric inclusion process. (United States)

    Reuveni, Shlomi; Eliazar, Iddo; Yechiali, Uri


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

  17. Asymmetric Imine Isomerisation in the Enantioselective Synthesis of Chiral Amines from Prochiral Ketones

    NARCIS (Netherlands)

    Willems, Johannes G.H.; Vries, Johannes G. de; Nolte, Roeland J.M.; Zwanenburg, Binne


    An asymmetric catalytic synthesis of chiral amines using a chiral base catalysed [1,3]-proton shift reaction of imines is described. The isomerisation reaction of N-benzylimines derived from prochiral ketones (benzylacetone, acetophenone) and p-substituted benzylamines, is catalysed by chiral

  18. Chiral bicycle imidazole nucleophilic catalysts: rational design, facile synthesis, and successful application in asymmetric Steglich rearrangement. (United States)

    Zhang, Zhenfeng; Xie, Fang; Jia, Jia; Zhang, Wanbin


    A new type of chiral bicycle imidazole nucleophilic catalyst was rationally designed, facilely synthesized, and successfully applied in an asymmetric Steglich rearrangement with good to excellent yield and enantioselectivity at ambient temperature. Moreover, it can be easily recycled with almost no reduction of catalytic efficiency. This is the first example for the successful chiral imidazole nucleophilic catalyst without H-bonding assistance.

  19. Rich catalytic injection (United States)

    Veninger, Albert [Coventry, CT


    A gas turbine engine includes a compressor, a rich catalytic injector, a combustor, and a turbine. The rich catalytic injector includes a rich catalytic device, a mixing zone, and an injection assembly. The injection assembly provides an interface between the mixing zone and the combustor. The injection assembly can inject diffusion fuel into the combustor, provides flame aerodynamic stabilization in the combustor, and may include an ignition device.

  20. Symmetric Decomposition of Asymmetric Games. (United States)

    Tuyls, Karl; Pérolat, Julien; Lanctot, Marc; Ostrovski, Georg; Savani, Rahul; Leibo, Joel Z; Ord, Toby; Graepel, Thore; Legg, Shane


    We introduce new theoretical insights into two-population asymmetric games allowing for an elegant symmetric decomposition into two single population symmetric games. Specifically, we show how an asymmetric bimatrix game (A,B) can be decomposed into its symmetric counterparts by envisioning and investigating the payoff tables (A and B) that constitute the asymmetric game, as two independent, single population, symmetric games. We reveal several surprising formal relationships between an asymmetric two-population game and its symmetric single population counterparts, which facilitate a convenient analysis of the original asymmetric game due to the dimensionality reduction of the decomposition. The main finding reveals that if (x,y) is a Nash equilibrium of an asymmetric game (A,B), this implies that y is a Nash equilibrium of the symmetric counterpart game determined by payoff table A, and x is a Nash equilibrium of the symmetric counterpart game determined by payoff table B. Also the reverse holds and combinations of Nash equilibria of the counterpart games form Nash equilibria of the asymmetric game. We illustrate how these formal relationships aid in identifying and analysing the Nash structure of asymmetric games, by examining the evolutionary dynamics of the simpler counterpart games in several canonical examples.

  1. Minimal asymmetric dark matter

    Directory of Open Access Journals (Sweden)

    Sofiane M. Boucenna


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

  2. Asymmetric black dyonic holes

    Directory of Open Access Journals (Sweden)

    I. Cabrera-Munguia


    Full Text Available A 6-parametric asymptotically flat exact solution, describing a two-body system of asymmetric black dyons, is studied. The system consists of two unequal counterrotating Kerr–Newman black holes, endowed with electric and magnetic charges which are equal but opposite in sign, separated by a massless strut. The Smarr formula is generalized in order to take into account their contribution to the mass. The expressions for the horizon half-length parameters σ1 and σ2, as functions of the Komar parameters and of the coordinate distance, are displayed, and the thermodynamic properties of the two-body system are studied. Furthermore, the seven physical parameters satisfy a simple algebraic relation which can be understood as a dynamical scenario, in which the physical properties of one body are affected by the ones of the other body.

  3. Asymmetric Realized Volatility Risk

    Directory of Open Access Journals (Sweden)

    David E. Allen


    Full Text Available In this paper, we document that realized variation measures constructed from high-frequency returns reveal a large degree of volatility risk in stock and index returns, where we characterize volatility risk by the extent to which forecasting errors in realized volatility are substantive. Even though returns standardized by ex post quadratic variation measures are nearly Gaussian, this unpredictability brings considerably more uncertainty to the empirically relevant ex ante distribution of returns. Explicitly modeling this volatility risk is fundamental. We propose a dually asymmetric realized volatility model, which incorporates the fact that realized volatility series are systematically more volatile in high volatility periods. Returns in this framework display time varying volatility, skewness and kurtosis. We provide a detailed account of the empirical advantages of the model using data on the S&P 500 index and eight other indexes and stocks.

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

    KAUST Repository

    Ajitha, Manjaly John


    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.

  5. Asymmetric Propargylation of Ketones using Allenylboronates Catalyzed by Chiral Biphenols (United States)

    Barnett, David S.; Schaus, Scott E.


    Chiral biphenols catalyze the enantioselective asymmetric propargylation of ketones using allenylboronates. The reaction uses 10 mol % of 3,3′-Br2-BINOL as the catalyst and allenyldioxoborolane as the nucleophile, in the absence of solvent, and under microwave irradiation to afford the homopropargylic alcohol. The reaction products are obtained in good yields (60 – 98%) and high enantiomeric ratios (3:1 – 99:1). Diastereoselective propargylations using chiral racemic allenylboronates result in good diastereoselectivities (dr > 86:14) and enantioselectivities (er > 92:8) under the catalytic conditions. PMID:21732609

  6. Asymmetric bifurcated halogen bonds. (United States)

    Novák, Martin; Foroutan-Nejad, Cina; Marek, Radek


    Halogen bonding (XB) is being extensively explored for its potential use in advanced materials and drug design. Despite significant progress in describing this interaction by theoretical and experimental methods, the chemical nature remains somewhat elusive, and it seems to vary with the selected system. In this work we present a detailed DFT analysis of three-center asymmetric halogen bond (XB) formed between dihalogen molecules and variously 4-substituted 1,2-dimethoxybenzene. The energy decomposition, orbital, and electron density analyses suggest that the contribution of electrostatic stabilization is comparable with that of non-electrostatic factors. Both terms increase parallel with increasing negative charge of the electron donor molecule in our model systems. Depending on the orientation of the dihalogen molecules, this bifurcated interaction may be classified as 'σ-hole - lone pair' or 'σ-hole - π' halogen bonds. Arrangement of the XB investigated here deviates significantly from a recent IUPAC definition of XB and, in analogy to the hydrogen bonding, the term bifurcated halogen bond (BXB) seems to be appropriate for this type of interaction.

  7. Magnetically Modified Asymmetric Supercapacitors Project (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. Scaleable, High Efficiency Microchannel Sabatier Reactor Project (United States)

    National Aeronautics and Space Administration — A Microchannel Sabatier Reactor System (MSRS) consisting of cross connected arrays of isothermal or graded temperature reactors is proposed. The reactor array...

  9. Asymmetric Flexible Supercapacitor Stack (United States)


    Electrical double layer supercapacitor is very significant in the field of electrical energy storage which can be the solution for the current revolution in the electronic devices like mobile phones, camera flashes which needs flexible and miniaturized energy storage device with all non-aqueous components. The multiwalled carbon nanotubes (MWNTs) have been synthesized by catalytic chemical vapor deposition technique over hydrogen decrepitated Mischmetal (Mm) based AB3alloy hydride. The polymer dispersed MWNTs have been obtained by insitu polymerization and the metal oxide/MWNTs were synthesized by sol-gel method. Morphological characterizations of polymer dispersed MWNTs have been carried out using scanning electron microscopy (SEM), transmission electron microscopy (TEM and HRTEM). An assymetric double supercapacitor stack has been fabricated using polymer/MWNTs and metal oxide/MWNTs coated over flexible carbon fabric as electrodes and nafion®membrane as a solid electrolyte. Electrochemical performance of the supercapacitor stack has been investigated using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy.

  10. Asymmetric Flexible Supercapacitor Stack

    Directory of Open Access Journals (Sweden)

    Leela Mohana Reddy A


    Full Text Available AbstractElectrical double layer supercapacitor is very significant in the field of electrical energy storage which can be the solution for the current revolution in the electronic devices like mobile phones, camera flashes which needs flexible and miniaturized energy storage device with all non-aqueous components. The multiwalled carbon nanotubes (MWNTs have been synthesized by catalytic chemical vapor deposition technique over hydrogen decrepitated Mischmetal (Mm based AB3alloy hydride. The polymer dispersed MWNTs have been obtained by insitu polymerization and the metal oxide/MWNTs were synthesized by sol-gel method. Morphological characterizations of polymer dispersed MWNTs have been carried out using scanning electron microscopy (SEM, transmission electron microscopy (TEM and HRTEM. An assymetric double supercapacitor stack has been fabricated using polymer/MWNTs and metal oxide/MWNTs coated over flexible carbon fabric as electrodes and nafion®membrane as a solid electrolyte. Electrochemical performance of the supercapacitor stack has been investigated using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy.

  11. Asymmetric Gepner models (revisited)

    Energy Technology Data Exchange (ETDEWEB)

    Gato-Rivera, B. [NIKHEF Theory Group, Kruislaan 409, 1098 SJ Amsterdam (Netherlands)] [Instituto de Fisica Fundamental, CSIC, Serrano 123, Madrid 28006 (Spain); Schellekens, A.N., E-mail: t58@nikhef.n [NIKHEF Theory Group, Kruislaan 409, 1098 SJ Amsterdam (Netherlands)] [Instituto de Fisica Fundamental, CSIC, Serrano 123, Madrid 28006 (Spain)] [IMAPP, Radboud Universiteit, Nijmegen (Netherlands)


    We reconsider a class of heterotic string theories studied in 1989, based on tensor products of N=2 minimal models with asymmetric simple current invariants. We extend this analysis from (2,2) and (1,2) spectra to (0,2) spectra with SO(10) broken to the Standard Model. In the latter case the spectrum must contain fractionally charged particles. We find that in nearly all cases at least some of them are massless. However, we identify a large subclass where the fractional charges are at worst half-integer, and often vector-like. The number of families is very often reduced in comparison to the 1989 results, but there are no new tensor combinations yielding three families. All tensor combinations turn out to fall into two classes: those where the number of families is always divisible by three, and those where it is never divisible by three. We find an empirical rule to determine the class, which appears to extend beyond minimal N=2 tensor products. We observe that distributions of physical quantities such as the number of families, singlets and mirrors have an interesting tendency towards smaller values as the gauge groups approaches the Standard Model. We compare our results with an analogous class of free fermionic models. This displays similar features, but with less resolution. Finally we present a complete scan of the three family models based on the triply-exceptional combination (1,16{sup *},16{sup *},16{sup *}) identified originally by Gepner. We find 1220 distinct three family spectra in this case, forming 610 mirror pairs. About half of them have the gauge group SU(3)xSU(2){sub L}xSU(2){sub R}xU(1){sup 5}, the theoretical minimum, and many others are trinification models.

  12. Catalytic distillation process (United States)

    Smith, L.A. Jr.


    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  13. Catalytic distillation structure (United States)

    Smith, L.A. Jr.


    Catalytic distillation structure is described for use in reaction distillation columns, and provides reaction sites and distillation structure consisting of a catalyst component and a resilient component intimately associated therewith. The resilient component has at least about 70 volume % open space and is present with the catalyst component in an amount such that the catalytic distillation structure consists of at least 10 volume % open space. 10 figs.

  14. Asymmetric catalysis in aqueous media: use of metal-chiral crown ethers as efficient chiral Lewis acid catalysts in asymmetric aldol reactions

    Directory of Open Access Journals (Sweden)

    Shu Kobayashi


    Full Text Available Metal-chiral crown ether complexes have been developed as efficient chiral Lewis acid catalysts for asymmetric aldol reactions of silyl enol ethers with aldehydes in aqueous media. While many excellent catalytic asymmetric reactions have been developed recently, most of them have to be carried out under strictly anhydrous conditions in organic solvents. This is probably due to the instability of many catalysts and/or intermediates in the presence of even a small amount of water. To address this issue, we searched for metal-crown ether complexes on the basis of our "multi-coordination" hypothesis, and found that lead(II and lanthanide(III catalysts worked well as chiral Lewis acids in aqueous media. To the best of our knowledge, these are the first examples of chiral crown-based Lewis acids that can be successfully used in catalytic asymmetric reactions. The catalysts have been characterized by X-ray diffraction, and their unique structures as chiral catalysts have been revealed. Use of water as a solvent is essential in these asymmetric catalysis, and the role of water on these reactions to explain the high reactivity and selectivity has been suggested. Another important point is that kinetic studies have shown the possibility that these types of crown ether complexes would be suitable as chiral catalysts employed in aqueous media. In addition, although the catalytic asymmetric aldol reactions are one of the most powerful carbon-carbon bond-forming methodologies and several successful examples have been reported, the use of aprotic anhydrous solvents and low reaction temperatures (-78 °C has been needed in almost all successful cases. On the other hand, the present reactions proceeded smoothly at -10-0 °C in water-alcohol solutions while retaining high levels of diastereo- and enantioselectivities.

  15. Controlling stereochemical outcomes of asymmetric processes by catalyst remote molecular functionalizations: chiral diamino-oligothiophenes (DATs) as ligands in asymmetric catalysis. (United States)

    Albano, Vincenzo Giulio; Bandini, Marco; Barbarella, Giovanna; Melucci, Manuela; Monari, Magda; Piccinelli, Fabio; Tommasi, Simona; Umani-Ronchi, Achille


    The synthesis, characterization, and structure-guided application of a new class of highly versatile chiral C(2)-symmetric diamine-oligothiophene ligands in Pd-catalyzed asymmetric transformations are presented. Experimental investigations of the intimate role of pendant pi-conjugate oligothiophenes in determining the catalytic activity of the corresponding chiral Pd complexes are described. Their unusual behavior opens up new routes toward the logical design of finely tuned organometallic catalysts by remote structural functionalizations.

  16. Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

    Directory of Open Access Journals (Sweden)

    Marina Rubina


    Full Text Available A novel class of chiral phosphanyl-oxazoline (PHOX ligands with a conformationally rigid cyclopropyl backbone was synthesized and tested in the intermolecular asymmetric Heck reaction. Mechanistic modelling and crystallographic studies were used to predict the optimal ligand structure and helped to design a very efficient and highly selective catalytic system. Employment of the optimized ligands in the asymmetric arylation of cyclic olefins allowed for achieving high enantioselectivities and significantly suppressing product isomerization. Factors affecting the selectivity and the rate of the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands.

  17. A graphene-based smart catalytic system with superior catalytic performances and temperature responsive catalytic behaviors. (United States)

    Qi, Junjie; Lv, Weipeng; Zhang, Guanghui; Li, Yang; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin


    We have successfully developed a unique graphene-based smart catalytic system which consists of the graphene supported Au-Pt bimetallic nanocatalyst with a well-defined core-shell structure and a dextran-based temperature-responsive polymer. The unique catalytic system possesses excellent catalytic performances and the catalytic activities could be readily switched on or off at different temperature windows.

  18. Asymmetric distances for binary embeddings. (United States)

    Gordo, Albert; Perronnin, Florent; Gong, Yunchao; Lazebnik, Svetlana


    In large-scale query-by-example retrieval, embedding image signatures in a binary space offers two benefits: data compression and search efficiency. While most embedding algorithms binarize both query and database signatures, it has been noted that this is not strictly a requirement. Indeed, asymmetric schemes that binarize the database signatures but not the query still enjoy the same two benefits but may provide superior accuracy. In this work, we propose two general asymmetric distances that are applicable to a wide variety of embedding techniques including locality sensitive hashing (LSH), locality sensitive binary codes (LSBC), spectral hashing (SH), PCA embedding (PCAE), PCAE with random rotations (PCAE-RR), and PCAE with iterative quantization (PCAE-ITQ). We experiment on four public benchmarks containing up to 1M images and show that the proposed asymmetric distances consistently lead to large improvements over the symmetric Hamming distance for all binary embedding techniques.

  19. Asymmetric cation-binding catalysis

    DEFF Research Database (Denmark)

    Oliveira, Maria Teresa; Lee, Jiwoong


    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...... and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation-binding catalysis was recently expanded to silicon-based reagents, enabling...

  20. Does asymmetric correlation affect portfolio optimization? (United States)

    Fryd, Lukas


    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.

  1. Hydroxamic acids in asymmetric synthesis. (United States)

    Li, Zhi; Yamamoto, Hisashi


    Metal-catalyzed stereoselective reactions are a central theme in organic chemistry research. In these reactions, the stereoselection is achieved predominantly by introducing chiral ligands at the metal catalyst's center. For decades, researchers have sought better chiral ligands for asymmetric catalysis and have made great progress. Nevertheless, to achieve optimal stereoselectivity and to catalyze new reactions, new chiral ligands are needed. Because of their high metal affinity, hydroxamic acids play major roles across a broad spectrum of fields from biochemistry to metal extraction. Dr. K. Barry Sharpless first revealed their potential as chiral ligands for asymmetric synthesis in 1977: He published the chiral vanadium-hydroxamic-acid-catalyzed, enantioselective epoxidation of allylic alcohols before his discovery of Sharpless asymmetric epoxidation, which uses the titanium-tartrate complex as the chiral reagent. However, researchers have reported few highly enantioselective reactions using metal-hydroxamic acid as catalysts since then. This Account summarizes our research on metal-catalyzed asymmetric epoxidation using hydroxamic acids as chiral ligands. We designed and synthesized a series of new hydroxamic acids, most notably the C2-symmetric bis-hydroxamic acid (BHA) family. V-BHA-catalyzed epoxidation of allylic and homoallylic alcohols achieved higher activity and stereoselectivity than Sharpless asymmetric epoxidation in many cases. Changing the metal species led to a series of unprecedented asymmetric epoxidation reactions, such as (i) single olefins and sulfides with Mo-BHA, (ii) homoallylic and bishomoallylic alcohols with Zr- and Hf-BHA, and (iii) N-alkenyl sulfonamides and N-sulfonyl imines with Hf-BHA. These reactions produce uniquely functionalized chiral epoxides with good yields and enantioselectivities.

  2. Nanocarbons for Catalytic Desulfurization. (United States)

    Gu, Qingqing; Lin, Yangming; Heumann, Saskia; Su, Dangsheng


    Nanocarbon catalysts are green and sustainable alternatives to metal-based catalysts for numerous catalytic transformations. The application of nanocarbons for environmental catalysis is an emerging research discipline and has undergone rapid development in recent years. In this focus review, we provide a critical analysis of state-of-the-art nanocarbon catalysts for three different catalytic desulfurization processes. In particular, we focus on the advantages and limitations as well as the reaction mechanisms of the nanocarbon catalysts at the molecular level. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Asymmetric hydrogenation using monodentate phosphoramidite ligands

    NARCIS (Netherlands)

    Minnaard, Adriaan J.; Feringa, Ben L.; Lefort, Laurent; De Vries, Johannes G.


    Monodentate phosphoramidites are excellent ligands for Rh-catalyzed asymmetric hydrogenations of substituted olefins. Enantioselectivities between 95 and 99% were obtained in the asymmetric hydrogenation of protected alpha- and beta-dehydroamino acids and esters, itaconic acid and esters, aromatic

  4. Asymmetric Synthesis via Chiral Aziridines

    DEFF Research Database (Denmark)

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


    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...

  5. Structure of asymmetrical peptide dendrimers

    NARCIS (Netherlands)

    Okrugin, B.M.; Neelov, I.M.; Leermakers, F.A.M.; Borisov, Oleg V.


    Structural properties of asymmetric peptide dendrimers up to the 11th generation are studied on the basis of the self-consistent field Scheutjens-Fleer numerical approach. It is demonstrated that large scale properties such as, e.g., the gyration radius, are relatively weakly affected by the

  6. Synthesis of Main-Chain Chiral Quaternary Ammonium Polymers for Asymmetric Catalysis Using Quaternization Polymerization

    Directory of Open Access Journals (Sweden)

    Md. Masud Parvez


    Full Text Available Main-chain chiral quaternary ammonium polymers were successfully synthesized by the quaternization polymerization of cinchonidine dimer with dihalides. The polymerization occurred smoothly under optimized conditions to give novel type of main-chain chiral quaternary ammonium polymers. The catalytic activity of the polymeric chiral organocatalysts was investigated on the asymmetric benzylation of N-(diphenylmethylideneglycine tert-butyl ester.

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

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


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


    African Journals Online (AJOL)

    Based on the property that in 0.12 M sulfuric acid medium titanium(IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of titanium is


    African Journals Online (AJOL)

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    Research Center for Nanotechnology, Changchun University of Science and Technology,. Changchun 130022 ... Although catalytic kinetic spectrophotometry has been used in the determination of copper, the selectivity ... In this paper CPApA was used as the chromogenic agent, H2O2 as the oxidant, Cu(II) as the catalyst.

  10. The upside of downsizing: asymmetric trifunctional organocatalysts as small enzyme mimics for cooperative enhancement of both rate and enantioselectivity with regulation. (United States)

    Liu, Fei


    Small molecule organic catalysts (organocatalysts) are widely used in asymmetric catalysis and synthesis. Compared to their enzymatic and transition-metal counterparts, organocatalysts have advantages in catalytic scope and efficiency but are more limited in proficiency. Chiral trifunctional organocatalysts, in which multiple catalytic motifs act cooperatively on a chiral scaffold, are an emerging class of organocatalysts with improved proficiency. Cooperativity design that enables both enantioselectivity and rate enhancement is essential to developing future generations of organocatalysts in biomimetic asymmetric catalysis. © 2013 Wiley Periodicals, Inc.

  11. Cyclodextrins in Asymmetric and Stereospecific Synthesis

    Directory of Open Access Journals (Sweden)

    Fliur Macaev


    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.

  12. A Note on Asymmetric Thick Branes

    Directory of Open Access Journals (Sweden)

    D. Bazeia


    Full Text Available We study asymmetric thick braneworld scenarios, generated after adding a constant to the superpotential associated with the scalar field. We study in particular models with odd and even polynomial superpotentials, and we show that asymmetric brane can be generated irrespective of the potential being symmetric or asymmetric. We study in addition the nonpolynomial sine-Gordon like model, also constructed with the inclusion of a constant in the standard superpotential, and we investigate gravitational stability of the asymmetric brane. The results suggest robustness of the new braneworld scenarios and add further possibilities of the construction of asymmetric branes.

  13. Geodesics in Asymmetric Metric Spaces

    Directory of Open Access Journals (Sweden)

    Mennucci Andrea C. G.


    Full Text Available In a recent paper [17] we studied asymmetric metric spaces; in this context we studied the length of paths, introduced the class of run-continuous paths; and noted that there are different definitions of “length spaces” (also known as “path-metric spaces” or “intrinsic spaces”. In this paper we continue the analysis of asymmetric metric spaces.We propose possible definitions of completeness and (local compactness.We define the geodesics using as admissible paths the class of run-continuous paths.We define midpoints, convexity, and quasi-midpoints, but without assuming the space be intrinsic.We distinguish all along those results that need a stronger separation hypothesis. Eventually we discuss how the newly developed theory impacts the most important results, such as the existence of geodesics, and the renowned Hopf-Rinow (or Cohn-Vossen theorem.

  14. Electron Jet of Asymmetric Reconnection (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


    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.

  15. Asymmetric information and macroeconomic dynamics (United States)

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


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

  16. Comprehensive asymmetric dark matter model


    Lonsdale, Stephen J.; Volkas, Raymond R.


    Asymmetric dark matter (ADM) is motivated by the similar cosmological mass densities measured for ordinary and dark matter. We present a comprehensive theory for ADM that addresses the mass density similarity, going beyond the usual ADM explanations of similar number densities. It features an explicit matter-antimatter asymmetry generation mechanism, has one fully worked out thermal history and suggestions for other possibilities, and meets all phenomenological, cosmological and astrophysical...

  17. Up-down asymmetric tokamaks

    CERN Document Server

    Ball, Justin


    Bulk toroidal rotation has proven capable of stabilising both dangerous MHD modes and turbulence. In this thesis, we explore a method to drive rotation in large tokamaks: up-down asymmetry in the magnetic equilibrium. We seek to maximise this rotation by finding optimal up-down asymmetric flux surface shapes. First, we use the ideal MHD model to show that low order external shaping (e.g. elongation) is best for creating up-down asymmetric flux surfaces throughout the device. Then, we calculate realistic up-down asymmetric equilibria for input into nonlinear gyrokinetic turbulence analysis. Analytic gyrokinetics shows that, in the limit of fast shaping effects, a poloidal tilt of the flux surface shaping has little effect on turbulent transport. Since up-down symmetric surfaces do not transport momentum, this invariance to tilt implies that devices with mirror symmetry about any line in the poloidal plane will drive minimal rotation. Accordingly, further analytic investigation suggests that non-mirror symmetri...

  18. Catalytic Membranes Embedding Selective Catalysts: Preparation and Applications (United States)

    Drioli, Enrico; Fontananova, Enrica

    The embedding of a catalyst in membranes is today recognized as a promising strategy to develop highly efficient and eco-friendly heterogeneous catalytic chemical processes. When a catalyst is heterogenized within or on the surface of a membrane, the membrane composition (characteristics of the membrane material: hydrophobic or hydrophilic, presence of chemical groups with specific functionality, etc.) and the membrane structure (dense or porous, symmetric or asymmetric), can positively influence the catalyst performance, not only by the selective sorption and diffusion of reagents and/or products, but also influencing the catalyst activity by electronic and conformational effect. These effects are similar to those occurring in biological membranes. In this chapter, after a preliminary presentation of the basic principles of membrane reactors and polymer membranes, the preparation, characterization and applications of polymeric catalytic membranes, will be discussed.

  19. Polymer and Membrane Design for Low Temperature Catalytic Reactions

    KAUST Repository

    Villalobos, Luis Francisco


    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.

  20. A homochiral metal-organic framework as an effective asymmetric catalyst for cyanohydrin synthesis. (United States)

    Mo, Ke; Yang, Yuhua; Cui, Yong


    A homochiral metal-organic framework (MOF) of an enantiopure 2,2'-dihydroxy-1,1'-biphenyl ligand was constructed. After exchanging one proton of the dihydroxyl group for Li(I) ions, the framework is shown to be a highly efficient and recyclable heterogeneous catalyst for asymmetric cyanation of aldehydes with up to >99% ee. Compared with the homogeneous counterpart, the MOF catalyst exhibits significantly enhanced catalytic activity and enantioselectivity, especially at a low catalyst/substrate ratio, due to that the rigid framework could stabilize the catalytically active monolithium salt of biphenol against its free transformation to catalytically inactive and/or less active assemblies in reactions. The synthetic utility of the cyanation was demonstrated in the synthesis of (S)-bufuralol (a nonselective β-adrenoceptor blocking agent) with 98% ee.

  1. Asymmetric Michael Addition of Ketones to Nitroolefins Catalyzed by a Novel Chiral Pyrrolidine-Thiourea in the Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Jun [Suzhou Univ., Suzhou (China); Chen, Weiyi [J and K Suzhou Ultrafine Material Ltd, Suzhou (China)


    A novel chiral pyrrolidine-thiourea has been developed and successfully applied to the asymmetric Michael addition of ketones with nitroolefins in ionic liquid. The corresponding products could be obtained in good yields with good enantio- and diastereoselectivities of products. In addition, the chiral catalytic system could be reused with comparable catalytic activity and stereoselectivity. Further studies are under way to expand the synthetic utility of this new reaction, as well as the application of this catalytic system in other asymmetric transformations. Organocatalytic asymmetric reactions have proved to be efficient and powerful tools in organic synthesis. Among them, the asymmetric Michael reaction of nitroolefins with carbon nucleophiles is widely recognized as one of the most important and versatile processes for the synthesis of enantioselective C-C and C-X bonds; for the nitroolefins are of special interest as excellent Michael acceptors, and the nitro functionality can be easily transformed into an amine, nitrile oxide, ketone, carboxylic acid, hydrogen, etc., providing a wide range of synthetically interesting compounds.

  2. Catalytic reforming methods (United States)

    Tadd, Andrew R; Schwank, Johannes


    A catalytic reforming method is disclosed herein. The method includes sequentially supplying a plurality of feedstocks of variable compositions to a reformer. The method further includes adding a respective predetermined co-reactant to each of the plurality of feedstocks to obtain a substantially constant output from the reformer for the plurality of feedstocks. The respective predetermined co-reactant is based on a C/H/O atomic composition for a respective one of the plurality of feedstocks and a predetermined C/H/O atomic composition for the substantially constant output.

  3. LG tools for asymmetric wargaming (United States)

    Stilman, Boris; Yakhnis, Alex; Yakhnis, Vladimir


    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

  4. Loan sales under asymmetric information


    Vargas Martínez, Mónica


    Loans are illiquid assets that can be sold in a secondary market even that buyers have no certainty about their quality. I study a model in which a lender has access to new investment opportunities when all her assets are illiquid. To raise funds, the lender may either borrow using her assets as collateral, or she can sell them in a secondary market. Given asymmetric information about assets quality, the lender cannot recover the total value of her assets. There is then a role for the governm...

  5. Urinary catalytic iron in obesity

    National Research Council Canada - National Science Library

    Thethi, Tina K; Parsha, Kaushik; Rajapurkar, Mohan; Mukhopadhyay, Banibrata; Shah, Sudhir; Yau, C Lillian; Japa, Shanker; Fonseca, Vivian


    ...), hypertension, and chronic kidney disease. Catalytic iron, which has been associated with these chronic diseases, may be one of the links between obesity and these multifactorial diverse disorders...

  6. Novel Catalytic Membrane Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stuart Nemser, PhD


    There are many industrial catalytic organic reversible reactions with amines or alcohols that have water as one of the products. Many of these reactions are homogeneously catalyzed. In all cases removal of water facilitates the reaction and produces more of the desired chemical product. By shifting the reaction to right we produce more chemical product with little or no additional capital investment. Many of these reactions can also relate to bioprocesses. Given the large number of water-organic compound separations achievable and the ability of the Compact Membrane Systems, Inc. (CMS) perfluoro membranes to withstand these harsh operating conditions, this is an ideal demonstration system for the water-of-reaction removal using a membrane reactor. Enhanced reaction synthesis is consistent with the DOE objective to lower the energy intensity of U.S. industry 25% by 2017 in accord with the Energy Policy Act of 2005 and to improve the United States manufacturing competitiveness. The objective of this program is to develop the platform technology for enhancing homogeneous catalytic chemical syntheses.

  7. Asymmetric liberations in exterior resonances (United States)

    Beauge, C.


    The purpose of this paper is to present a general analysis of the planar circular restricted problem of three bodies in the case of exterior mean-motion resonances. Particularly, our aim is to map the phase space of various commensurabilities and determine the singular solutions of the averaged system, comparing them to the well-known case of interior resonances. In some commensurabilities (e.g. 1/2, 1/3) we show the existence of asymmetric librations; that is, librations in which the stationary value of the critical angle theta = (p+q) lambda1-p lambda-q pi is not equal to either zero or pi. The origin, stability and morphogenesis of these solutions are discussed and compared to symmetric librations. However, in some other resonances (e.g. 2/3, 3/4), these fixed points of the mean system seem to be absent. Librations in such cases are restricted to theta = O mod(pi). Asymmetric singular solutions of the plane circular problem are unknown in the case of interior resonances and cannot be reproduced by the reduced Andoyer Hamiltonian known as the Second Fundamental Model for Resonance. However, we show that the extended version of this Hamiltonian function, in which harmonics up to order two are considered, can reproduce fairly well the principal topological characteristics of the phase space and thereby constitutes a simple and useful analytical approximation for these resonances.

  8. Asymmetric Laguerre-Gaussian beams (United States)

    Kovalev, A. A.; Kotlyar, V. V.; Porfirev, A. P.


    We introduce a family of asymmetric Laguerre-Gaussian (aLG) laser beams. The beams have been derived via a complex-valued shift of conventional LG beams in the Cartesian plane. While propagating in a uniform medium, the first bright ring of the aLG beam becomes less asymmetric and the energy is redistributed toward peripheral diffraction rings. The projection of the orbital angular momentum (OAM) onto the optical axis is calculated. The OAM is shown to grow quadratically with increasing asymmetry parameter of the aLG beam, which equals the ratio of the shift to the waist radius. Conditions for the OAM becoming equal to the topological charge have been derived. For aLG beams with zero radial index, we have deduced an expression to define the intensity maximum coordinates and shown the crescent-shaped intensity pattern to rotate during propagation. Results of the experimental generation and rotation of aLG beams agree well with theoretical predictions.

  9. Thin lenses of asymmetric power

    Directory of Open Access Journals (Sweden)

    W. F. Harris


    Full Text Available It is generally supposed that thin systems, including refracting surfaces and thin lenses, have powers that are necessarily symmetric.  In other words they have powers which can be represented assymmetric dioptric power matrices and in the familar spherocylindrical form used in optometry and ophthalmology.  This paper shows that this is not correct and that it is indeed possible for a thin system to have a power that is not symmetric and which cannot be expressed in spherocylindrical form.  Thin systems of asymmetric power are illustratedby means of a thin lens that is modelled with small prisms and is chosen to have a dioptric power ma-trix that is antisymmetric.  Similar models can be devised for a thin system whose dioptric power matrix is any  2 2 ×  matrix.  Thus any power, symmetric, asymmetric or antisymmetric, is possible for a thin system.  In this sense our understanding of the power of thin systems is now complete.

  10. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is ...

  11. Catalytic enantioselective N-nitroso aldol reaction of γ,δ-unsaturated δ-lactones. (United States)

    Yanagisawa, Akira; Fujinami, Takeo; Oyokawa, Yu; Sugita, Takuya; Yoshida, Kazuhiro


    A catalytic asymmetric N-nitroso aldol reaction of γ,δ-didehydro-δ-lactones with nitrosoarenes was achieved using chiral tin dibromide as the chiral precatalyst and sodium ethoxide as the base precatalyst in the presence of ethanol. Optically active α-hydroxyamino ketones with up to 99% ee were regioselectively obtained in moderate to high yields from various δ-aryl-substituted γ,δ-didehydro-δ-valerolactones and o-substituted nitrosoarenes.

  12. Asymmetric Warfare and the Will to Win

    National Research Council Canada - National Science Library

    Herrera, Cary


    This thesis explores the will to win in asymmetric war. Asymmetric war, in which one side has an overwhelming advantage over its opponent, will likely be the war of the future for the United States in the post-Cold War uni-polar world...

  13. Renewable resource management under asymmetric information

    DEFF Research Database (Denmark)

    Jensen, Frank; Andersen, Peder; Nielsen, Max


    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. I...

  14. Asymmetric Quantum Codes on Toric Surfaces

    DEFF Research Database (Denmark)

    Hansen, Johan P.


    Asymmetric quantum error-correcting codes are quantum codes defined over biased quantum channels: qubit-flip and phase-shift errors may have equal or different probabilities. The code construction is the Calderbank-Shor-Steane construction based on two linear codes. We present families of toric...... surfaces, toric codes and associated asymmetric quantum error-correcting codes....

  15. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach


    Chauhan, Pankaj; Chimni, Swapandeep Singh


    Summary 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.

  16. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach (United States)

    Chauhan, Pankaj


    Summary 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. PMID:23243475

  17. Worst Asymmetrical Short-Circuit Current

    DEFF Research Database (Denmark)

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


    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...

  18. Mechanochemistry assisted asymmetric organocatalysis: A sustainable approach

    Directory of Open Access Journals (Sweden)

    Pankaj Chauhan


    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.

  19. Evolution of random catalytic networks

    Energy Technology Data Exchange (ETDEWEB)

    Fraser, S.M. [Santa Fe Inst., NM (United States); Reidys, C.M. [Santa Fe Inst., NM (United States)]|[Los Alamos National Lab., NM (United States)


    In this paper the authors investigate the evolution of populations of sequences on a random catalytic network. Sequences are mapped into structures, between which are catalytic interactions that determine their instantaneous fitness. The catalytic network is constructed as a random directed graph. They prove that at certain parameter values, the probability of some relevant subgraphs of this graph, for example cycles without outgoing edges, is maximized. Populations evolving under point mutations realize a comparatively small induced subgraph of the complete catalytic network. They present results which show that populations reliably discover and persist on directed cycles in the catalytic graph, though these may be lost because of stochastic effects, and study the effect of population size on this behavior.

  20. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik


    This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

  1. Asymmetric Digital Subscriber Line (ADSL

    Directory of Open Access Journals (Sweden)

    Slavko Šarić


    Full Text Available ADSL (Asymmetric Digital Subscriber Line is a technologythat allows transmission at 8.488 Mbps over the existingtelephone copper line (speed range depending on the distance.ADSL circuit connects the ADSL modems by twisted-pairtelephone lines creating three infonnation channels: high speedsimplex (maximum 9 Mbps, medium speed duplex channel(maximum 2 Mbps and plain old telephone service channel.ADSL technology supports up to seven synchronous channelsthat can be configured to meet the needs of the end user.One could simultaneously view four movies stored in MPEG 1fonnat on separate television sets (MPEG 1 transmitted at 1.5Mbps, hold a video-conference (transmitted at 348 kbps,download data files from a server at 128 kbps via ISDN andeven receive a telephone call.

  2. Research on asymmetric searchable encryption (United States)

    Yu, Zonghua; Wu, Yudong


    Cloud server side to ease the user's local storage pressure at the same time, there are hidden data on the hidden dangers, the user often choose to upload the data in the form of cipher text to the cloud server. However, the classic data encryption and decryption algorithms are not provided search function, affecting the user's efficiency. To this end, an asymmetric searchable encryption scheme is proposed. The scheme can be used for any person can generate a trapdoor, cipher text can be free modified, the key pair generated by the user themselves, encrypt the identity, S-shaped virtual and other five loopholes to improve. The analysis results show that the scheme solves the above five vulnerabilities in the original scheme, so that the information semantics of both parties of communication can be guaranteed.

  3. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.


    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  4. Catalytic cracking with deasphalted oil

    Energy Technology Data Exchange (ETDEWEB)

    Beaton, W.I.; Taylor, J.L.; Peck, L.B.; Mosby, J.F.


    This patent describes a catalytic cracking process. It comprises: hydrotreating resid; thereafter deasphalting the hydrotreated resid to produce substantially deasphalted oil; catalytically cracking the hydrotreated oil in a catalytic cracking unit in the presence of a cracking catalyst to produce upgraded oil leaving coked catalyst; and regenerating the coked catalyst in the presence of a combustion-supporting gas comprising excess molecular oxygen in an amount greater than the stoichiometric amount required for substantially completely combusting the coke on the catalyst to carbon dioxide.

  5. Catalytic cracking of lignites

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, M.; Nowak, S.; Naegler, T.; Zimmermann, J. [Hochschule Merseburg (Germany); Welscher, J.; Schwieger, W. [Erlangen-Nuernberg Univ. (Germany); Hahn, T. [Halle-Wittenberg Univ., Halle (Germany)


    A most important factor for the chemical industry is the availability of cheap raw materials. As the oil price of crude oil is rising alternative feedstocks like coal are coming into focus. This work, the catalytic cracking of lignite is part of the alliance ibi (innovative Braunkohlenintegration) to use lignite as a raw material to produce chemicals. With this new one step process without an input of external hydrogen, mostly propylene, butenes and aromatics and char are formed. The product yield depends on manifold process parameters. The use of acid catalysts (zeolites like MFI) shows the highest amount of the desired products. Hydrogen rich lignites with a molar H/C ratio of > 1 are to be favoured. Due to primary cracking and secondary reactions the ratio between catalyst and lignite, temperature and residence time are the most important parameter to control the product distribution. Experiments at 500 C in a discontinuous rotary kiln reactor show yields up to 32 wt-% of hydrocarbons per lignite (maf - moisture and ash free) and 43 wt-% char, which can be gasified. Particularly, the yields of propylene and butenes as main products can be enhanced four times to about 8 wt-% by the use of catalysts while the tar yield decreases. In order to develop this innovative process catalyst systems fixed on beads were developed for an easy separation and regeneration of the used catalyst from the formed char. (orig.)

  6. Industrial asymmetric synthesis by use of metal-BINAP catalysts; Kinzoku-BINAP sakutai shokubai wo mochiita fusai gosei gijutsu no kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    Kumobayashi, H.; Sayo, N.; Akutagawa, S.; Sakaguchi, T.; Tsuruta, H. [Takasago International Corporation, Kanagawa (Japan). Central Research Laboratory


    This article covers the history and present progress of the industrial asymmetric synthesis by use of BINAP (2,2`-bis(diphenylphosphino)-1,1`-binaphthyl)-metal catalysts. Especially, the historic discovery of the BINAP-rhodium(I)-catalyzed 1,3-hydrogen migration of N,N-diethylgeranylamine (GDEA) and the achievement of practical preparation of optically active BINAP, led to the establishment of the first industrial process for efficient production of l-menthol employing asymmetric catalysts. Continuing efforts have been devoted to the exploration of new catalytic reactions using new BINAP-metal complexes and their applications to industrial asymmetric synthesis. Among them, asymmetric hydrogenation of functionalyzed olefins and ketones by use of BINAP-ruthenium (II) complexes provides fruitful results. Today, a wide range of chiral compounds including the pharmaceutical intermediates 4-acetoxy-2-azetidinone (4-AA) and 1,2-propanediol (2-PPD) are produced in industrial scale in Takasago. 47 refs., 8 figs., 9 tabs.

  7. Modelling asymmetric growth in crowded plant communities

    DEFF Research Database (Denmark)

    Damgaard, Christian


    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....

  8. Nondeterministic self-assembly with asymmetric interactions (United States)

    Tesoro, S.; Göpfrich, K.; Kartanas, T.; Keyser, U. F.; Ahnert, S. E.


    We investigate general properties of nondeterministic self-assembly with asymmetric interactions, using a computational model and DNA tile assembly experiments. By contrasting symmetric and asymmetric interactions we show that the latter can lead to self-limiting cluster growth. Furthermore, by adjusting the relative abundance of self-assembly particles in a two-particle mixture, we are able to tune the final sizes of these clusters. We show that this is a fundamental property of asymmetric interactions, which has potential applications in bioengineering, and provides insights into the study of diseases caused by protein aggregation.

  9. Catalytic pyrolysis of lignocellulosic biomass

    NARCIS (Netherlands)

    Seshan, Kulathuiyer; Sa, Jacinto


    This chapter reports on the latest developments of biomass catalytic pyrolysis for the production of fuels. The primary focus is on the role of catalysts in the process, namely, their influence in the liquefaction of lignocellulosic biomass.

  10. Engineering reactors for catalytic reactions

    Indian Academy of Sciences (India)

    Chemical Engineering and Process Development Division, CSIR - National Chemical Laboratory,. Pune 411 008, India ... Abstract. Catalytic reactions are ubiquitous in chemical and allied industries. ... strategies and recent advances in process intensification/ multifunctional reactors are discussed to illustrate the approach.

  11. Catalytic Fast Pyrolysis: A Review


    Theodore Dickerson; Juan Soria


    Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using...

  12. Fuel-Rich Catalytic Combustion (United States)

    Brabbs, Theodore A.; Olson, Sandra L.


    Two-stage combustion system reduces particulate emissions. Program on catalytic oxidation of iso-octane demonstrates feasibility of two-stage combustion system for reducing particulate emissions. With fuel-rich (fuel/air equivalence ratios of 4.8 to 7.8) catalytic-combustion preburner as first stage, combustion process free of soot at reactor-outlet temperatures of 1,200 K or less.

  13. Modeling of asymmetrical boost converters

    Directory of Open Access Journals (Sweden)

    Eliana Isabel Arango Zuluaga


    Full Text Available The asymmetrical interleaved dual boost (AIDB is a fifth-order DC/DC converter designed to interface photovoltaic (PV panels. The AIDB produces small current harmonics to the PV panels, reducing the power losses caused by the converter operation. Moreover, the AIDB provides a large voltage conversion ratio, which is required to step-up the PV voltage to the large dc-link voltage used in grid-connected inverters. To reject irradiance and load disturbances, the AIDB must be operated in a closed-loop and a dynamic model is required. Given that the AIDB converter operates in Discontinuous Conduction Mode (DCM, classical modeling approaches based on Continuous Conduction Mode (CCM are not valid. Moreover, classical DCM modeling techniques are not suitable for the AIDB converter. Therefore, this paper develops a novel mathematical model for the AIDB converter, which is suitable for control-pur-poses. The proposed model is based on the calculation of a diode current that is typically disregarded. Moreover, because the traditional correction to the second duty cycle reported in literature is not effective, a new equation is designed. The model accuracy is contrasted with circuital simulations in time and frequency domains, obtaining satisfactory results. Finally, the usefulness of the model in control applications is illustrated with an application example.

  14. Modeling of asymmetrical boost converters

    Directory of Open Access Journals (Sweden)

    Eliana Isabel Arango Zuluaga


    Full Text Available The asymmetrical interleaved dual boost (AIDB is a fifth-order DC/DC converter designed to interface photovoltaic (PV panels. The AIDB produces small current harmonics to the PV panels, reducing the power losses caused by the converter operation. Moreover, the AIDB provides a large voltage conversion ratio, which is required to step-up the PV voltage to the large dc-link voltage used in grid-connected inverters. To reject irradiance and load disturbances, the AIDB must be operated in a closed-loop and a dynamic model is required. Given that the AIDB converter operates in Discontinuous Conduction Mode (DCM, classical modeling approaches based on Continuous Conduction Mode (CCM are not valid. Moreover, classical DCM modeling techniques are not suitable for the AIDB converter. Therefore, this paper develops a novel mathematical model for the AIDB converter, which is suitable for control-pur-poses. The proposed model is based on the calculation of a diode current that is typically disregarded. Moreover, because the traditional correction to the second duty cycle reported in literature is not effective, a new equation is designed. The model accuracy is contrasted with circuital simulations in time and frequency domains, obtaining satisfactory results. Finally, the usefulness of the model in control applications is illustrated with an application example.

  15. Catalytic organometallic anticancer complexes (United States)

    Dougan, Sarah J.; Habtemariam, Abraha; McHale, Sarah E.; Parsons, Simon; Sadler, Peter J.


    Organometallic complexes offer chemistry that is not accessible to purely organic molecules and, hence, potentially new mechanisms of drug action. We show here that the presence of both an iodido ligand and a σ-donor/π-acceptor phenylazopyridine ligand confers remarkable inertness toward ligand substitution on the half-sandwich “piano-stool” ruthenium arene complexes [(η6-arene)Ru(azpy)I]+ (where arene = p-cymene or biphenyl, and azpy = N,N-dimethylphenyl- or hydroxyphenyl-azopyridine) in aqueous solution. Surprisingly, despite this inertness, these complexes are highly cytotoxic to human ovarian A2780 and human lung A549 cancer cells. Fluorescence-trapping experiments in A549 cells suggest that the cytotoxicity arises from an increase in reactive oxygen species. Redox activity of these azopyridine RuII complexes was confirmed by electrochemical measurements. The first one-electron reduction step (half-wave potential −0.2 to −0.4 V) is assignable to reduction of the azo group of the ligand. In contrast, the unbound azopyridine ligands are not readily reduced. Intriguingly the ruthenium complex acted as a catalyst in reactions with the tripeptide glutathione (γ-l-Glu-l-Cys-Gly), a strong reducing agent present in cells at millimolar concentrations; millimolar amounts of glutathione were oxidized to glutathione disulfide in the presence of micromolar ruthenium concentrations. A redox cycle involving glutathione attack on the azo bond of coordinated azopyridine is proposed. Such ligand-based redox reactions provide new concepts for the design of catalytic drugs. PMID:18687892

  16. Asymmetrical Warfare, Transformation, and Foreign Language Capability

    National Research Council Canada - National Science Library

    Porter, Clifford F


    .... There is no doubt that the current global war on terrorism is an asymmetrical war against an unpredictable enemy rather than the predictable or symmetrical threats against self-important dictators or the Soviet Union...

  17. Asymmetric cryptography based on wavefront sensing. (United States)

    Peng, Xiang; Wei, Hengzheng; Zhang, Peng


    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.

  18. Congenital asymmetric crying face: a case report

    Directory of Open Access Journals (Sweden)

    Semra Kara


    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.

  19. Modeling Asymmetric Volatility In Oil Prices

    National Research Council Canada - National Science Library

    Syed Aun Hassan


    .... The paper uses daily crude oil price data for the past 10 years to test and model the oil price volatility by fitting different variations of GARCH including a univariate asymmetric GARCH model to the series...

  20. Asymmetric dense matter in holographic QCD

    Directory of Open Access Journals (Sweden)

    Shin Ik Jae


    Full Text Available We study asymmetric dense matter in holographic QCD.We construct asymmetric dense matter by considering two quark flavor branes with dierent quark masses in a D4/D6/D6 model. To calculate the symmetry energy in nuclear matter, we consider two quarks with equal masses and observe that the symmetry energy increases with the total charge showing the stiff dependence. This behavior is universal in the sense that the result is independent of parameters in the model. We also study strange (or hyperon matter with one light and one intermediate mass quarks. In addition to the vacuum properties of asymmetric matter, we calculate meson masses in asymmetric dense matter and discuss our results in the light of in-medium kaon masses.

  1. Designing Asymmetric Multiferroics with Strong Magnetoelectric Coupling


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


    Multiferroics offer exciting opportunities for electric-field control of magnetism. Unfortunately, single-phase multiferroics suitable for such applications at room temperature has not been discovered. Here, we propose the concept of a new type of multiferroics, namely, "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 ...

  2. Stable Bound States of Asymmetric Dark Matter


    Wise, Mark B.; Zhang, Yue


    The simplest renormalizable effective field theories with asymmetric dark matter bound states contain two additional gauge singlet fields one being the dark matter and the other a mediator particle that the dark matter annihilates into. We examine the physics of one such model with a Dirac fermion as the dark matter and a real scalar mediator. For a range of parameters the Yukawa coupling of the dark matter to the mediator gives rise to stable asymmetric dark matter bound states. We derive pr...

  3. Kinetics and mechanism of vanadium catalysed asymmetric cyanohydrin synthesis in propylene carbonate. (United States)

    North, Michael; Omedes-Pujol, Marta


    Propylene carbonate can be used as a green solvent for the asymmetric synthesis of cyanohydrin trimethylsilyl ethers from aldehydes and trimethylsilyl cyanide catalysed by VO(salen)NCS, though reactions are slower in this solvent than the corresponding reactions carried out in dichloromethane. A mechanistic study has been undertaken, comparing the catalytic activity of VO(salen)NCS in propylene carbonate and dichloromethane. Reactions in both solvents obey overall second-order kinetics, the rate of reaction being dependent on the concentration of both the aldehyde and trimethylsilyl cyanide. The order with respect to VO(salen)NCS was determined and found to decrease from 1.2 in dichloromethane to 1.0 in propylene carbonate, indicating that in propylene carbonate, VO(salen)NCS is present only as a mononuclear species, whereas in dichloromethane dinuclear species are present which have previously been shown to be responsible for most of the catalytic activity. Evidence from ⁵¹V NMR spectroscopy suggested that propylene carbonate coordinates to VO(salen)NCS, blocking the free coordination site, thus inhibiting its Lewis acidity and accounting for the reduction in catalytic activity. This explanation was further supported by a Hammett analysis study, which indicated that Lewis base catalysis made a much greater contribution to the overall catalytic activity of VO(salen)NCS in propylene carbonate than in dichloromethane.

  4. Characteristics of Braced Excavation under Asymmetrical Loads

    Directory of Open Access Journals (Sweden)

    Changjie Xu


    Full Text Available Numerous excavation practices have shown that large discrepancies exist between field monitoring data and calculated results when the conventional symmetry-plane method (with half-width is used to design the retaining structure under asymmetrical loads. To examine the characteristics of a retaining structure under asymmetrical loads, we use the finite element method (FEM to simulate the excavation process under four different groups of asymmetrical loads and create an integrated model to tackle this problem. The effects of strut stiffness and wall length are also investigated. The results of numerical analysis clearly imply that the deformation and bending moment of diaphragm walls are distinct on different sides, indicating the need for different rebar arrangements when the excavation is subjected to asymmetrical loads. This study provides a practical approach to designing excavations under asymmetrical loads. We analyze and compare the monitoring and calculation data at different excavation stages and find some general trends. Several guidelines on excavation design under asymmetrical loads are drawn.

  5. Asymmetric Bessel-Gauss beams. (United States)

    Kotlyar, V V; Kovalev, A A; Skidanov, R V; Soifer, V A


    We propose a three-parameter family of asymmetric Bessel-Gauss (aBG) beams with integer and fractional orbital angular momentum (OAM). The aBG beams are described by the product of a Gaussian function by the nth-order Bessel function of the first kind of complex argument, having finite energy. The aBG beam's asymmetry degree depends on a real parameter c≥0: at c=0, the aBG beam is coincident with a conventional radially symmetric Bessel-Gauss (BG) beam; with increasing c, the aBG beam acquires a semicrescent shape, then becoming elongated along the y axis and shifting along the x axis for c≫1. In the initial plane, the intensity distribution of the aBG beams has a countable number of isolated optical nulls on the x axis, which result in optical vortices with unit topological charge and opposite signs on the different sides of the origin. As the aBG beam propagates, the vortex centers undergo a nonuniform rotation with the entire beam about the optical axis (c≫1), making a π/4 turn at the Rayleigh range and another π/4 turn after traveling the remaining distance. At different values of the c parameter, the optical nulls of the transverse intensity distribution change their position, thus changing the OAM that the beam carries. An isolated optical null on the optical axis generates an optical vortex with topological charge n. A vortex laser beam shaped as a rotating semicrescent has been generated using a spatial light modulator.

  6. Primary amine/CSA ion pair: A powerful catalytic system for the asymmetric enamine catalysis

    KAUST Repository

    Liu, Chen


    A novel ion pair catalyst containing a chiral counteranion can be readily derived by simply mixing cinchona alkaloid-derived diamine with chiral camphorsulfonic acid (CSA). A mixture of 9-amino(9-deoxy)epi-quinine 8 and (-)-CSA was found to be the best catalyst with matching chirality, enabling the direct amination of α-branched aldehydes to proceed in quantitative yields and with nearly perfect enantioselectivities. A 0.5 mol % catalyst loading was sufficient to catalyze the reaction, and a gram scale enantioselective synthesis of biologically important α-methyl phenylglycine has been successfully demonstrated. © 2011 American Chemical Society.

  7. Catalytic Asymmetric Reactions for Organic Synthesis: The Combined C-H Activation/Cope Rearrangement

    National Research Council Canada - National Science Library

    Huw M. L. Davies; Qihui Jin; Jack Halpern


    .... This article describes the synthetic utility of the combined C-H activation/Cope rearrangement, achieved by dirhodium tetraprolinate-catalyzed reaction of vinyldiazoacetates with compounds containing allylic C-H bonds...

  8. Toolbox approach to the search for effective ligands for catalytic asymmetric Cr-mediated coupling reactions. (United States)

    Guo, Haibing; Dong, Cheng-Guo; Kim, Dae-Shik; Urabe, Daisuke; Wang, Jiashi; Kim, Joseph T; Liu, Xiang; Sasaki, Takeo; Kishi, Yoshito


    Chromium catalysts derived from chiral sulfonamides represented by A effect the couplings of aldehydes with vinyl, allyl, or alkyl halides. With three distinct sites for structural modification, A affords access to a structurally diverse pool of chiral sulfonamides. The Cr catalysts derived from these sulfonamides exhibit a broad range of catalyst-substrate matching profiles. A strategy is presented to search for a satisfactory chiral sulfonamide for a given substrate. In order to demonstrate the generality and effectiveness of this approach, five diverse C-C bond-forming cases have been selected from the halichondrin synthesis. For each of the cases, two ligands have been deliberately searched for, to induce the formation of (R)- and (S)-alcohols, respectively, at the arbitrarily chosen efficiency level of ">or=80% yield with >or=20:1 stereoselectivity in the presence of

  9. Catalytic bioreactors and methods of using same

    Energy Technology Data Exchange (ETDEWEB)

    Worden, Robert Mark; Liu, Yangmu Chloe


    Various embodiments provide a bioreactor for producing a bioproduct comprising one or more catalytically active zones located in a housing and adapted to keep two incompatible gaseous reactants separated when in a gas phase, wherein each of the one or more catalytically active zones may comprise a catalytic component retainer and a catalytic component retained within and/or thereon. Each of the catalytically active zones may additionally or alternatively comprise a liquid medium located on either side of the catalytic component retainer. Catalytic component may include a microbial cell culture located within and/or on the catalytic component retainer, a suspended catalytic component suspended in the liquid medium, or a combination thereof. Methods of using various embodiments of the bioreactor to produce a bioproduct, such as isobutanol, are also provided.

  10. Catalytic distillation extends its reach

    Energy Technology Data Exchange (ETDEWEB)

    Rock, K.; McGuirk, T. [Catalytic Distillation Technologies, Houston, TX (United States); Gildert, G.R. [Catalytic Distillation Technologies, Pasadena, TX (United States)


    Since the early 1980s, catalytic distillation processes have been selected by more than a hundred operators for various applications. Since such a unit performs both reaction and distillation simultaneously, a combined column can replace a separate, fixed-bed reactor and distillation column, thereby eliminating equipment and reducing capital costs. And, compared to the conventional approach, catalytic distillation may also improve other factors, such as reactant conversion, selectivity, mass transfer, operating pressure, oligomer formation and catalyst fouling. The constant washing of the catalyst by liquid flowing down the column and the distillation of high-boiling foulants results in extended catalyst life. Four selective hydrogenation applications of catalytic distillation are discussed: Butadiene selective hydrogenation combined within an MTBE unit; Pentadiene selective hydrogenation; C{sub 4} acetylene conversion; and Benzene saturation.

  11. Catalytic activity of Au nanoparticles

    DEFF Research Database (Denmark)

    Larsen, Britt Hvolbæk; Janssens, Ton V.W.; Clausen, Bjerne


    Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change with par......Au is usually viewed as an inert metal, but surprisingly it has been found that Au nanoparticles less than 3–5 nm in diameter are catalytically active for several chemical reactions. We discuss the origin of this effect, focusing on the way in which the chemical activity of Au may change...... with particle size. We find that the fraction of low-coordinated Au atoms scales approximately with the catalytic activity, suggesting that atoms on the corners and edges of Au nanoparticles are the active sites. This effect is explained using density functional calculations....

  12. Asymmetrical soft palate cleft repair: preliminary results. (United States)

    Bütow, K-W; Engelbrecht, H; Naidoo, S


    The reconstructions of the asymmetrical soft palate cleft is a surgical challenge when it comes to achieving symmetry and optimal soft palate muscular function. Three different versions of the intravelar veloplasty have been used: the intravelar veloplasty (1969) (type I), the modification according to anatomical defects (1991) (type II), and the modification using part of Sommerlad's technique and part of Ivanov's technique (2008) (type III). The perioperative outcomes of the type II and type III intravelar veloplasty were assessed and compared in asymmetrical cleft cases. Two hundred and seventy-seven soft palate clefts were reconstructed: 153 type II and 124 type III. Of these, 49 were asymmetrical (17.7%); 23 underwent the type II procedure and 26 the type III procedure. Of the type II procedure cases, 30.4% remained asymmetrical postoperatively compared to 3.8% of the type III cases. The uvula appeared subjectively atrophic in 47.8% of the type II cases and in 7.7% of type III cases. Oro-nasal fistula occurred in 13.0% of the type II cases and 3.8% of the type III cases. Speech results will only be assessed after 4 years of age. The type III modified intravelar veloplasty has had a major beneficial impact on patients who had an asymmetrical soft palate cleft. Copyright © 2014. Published by Elsevier Ltd.

  13. Control of apoptosis by asymmetric cell division. (United States)

    Hatzold, Julia; Conradt, Barbara


    Asymmetric cell division and apoptosis (programmed cell death) are two fundamental processes that are important for the development and function of multicellular organisms. We have found that the processes of asymmetric cell division and apoptosis can be functionally linked. Specifically, we show that asymmetric cell division in the nematode Caenorhabditis elegans is mediated by a pathway involving three genes, dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail, that directly control the enzymatic machinery responsible for apoptosis. Interestingly, the MIDA1-like protein GlsA of the alga Volvox carteri, as well as the Snail-related proteins Snail, Escargot, and Worniu of Drosophila melanogaster, have previously been implicated in asymmetric cell division. Therefore, C. elegans dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail may be components of a pathway involved in asymmetric cell division that is conserved throughout the plant and animal kingdoms. Furthermore, based on our results, we propose that this pathway directly controls the apoptotic fate in C. elegans, and possibly other animals as well.

  14. Control of apoptosis by asymmetric cell division.

    Directory of Open Access Journals (Sweden)

    Julia Hatzold


    Full Text Available Asymmetric cell division and apoptosis (programmed cell death are two fundamental processes that are important for the development and function of multicellular organisms. We have found that the processes of asymmetric cell division and apoptosis can be functionally linked. Specifically, we show that asymmetric cell division in the nematode Caenorhabditis elegans is mediated by a pathway involving three genes, dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail, that directly control the enzymatic machinery responsible for apoptosis. Interestingly, the MIDA1-like protein GlsA of the alga Volvox carteri, as well as the Snail-related proteins Snail, Escargot, and Worniu of Drosophila melanogaster, have previously been implicated in asymmetric cell division. Therefore, C. elegans dnj-11 MIDA1, ces-2 HLF, and ces-1 Snail may be components of a pathway involved in asymmetric cell division that is conserved throughout the plant and animal kingdoms. Furthermore, based on our results, we propose that this pathway directly controls the apoptotic fate in C. elegans, and possibly other animals as well.

  15. A sampling theory for asymmetric communities. (United States)

    Noble, Andrew E; Temme, Nico M; Fagan, William F; Keitt, Timothy H


    We introduce the first analytical model of asymmetric community dynamics to yield Hubbell's neutral theory in the limit of functional equivalence among all species. Our focus centers on an asymmetric extension of Hubbell's local community dynamics, while an analogous extension of Hubbell's metacommunity dynamics is deferred to an appendix. We find that mass-effects may facilitate coexistence in asymmetric local communities and generate unimodal species abundance distributions indistinguishable from those of symmetric communities. Multiple modes, however, only arise from asymmetric processes and provide a strong indication of non-neutral dynamics. Although the exact stationary distributions of fully asymmetric communities must be calculated numerically, we derive approximate sampling distributions for the general case and for nearly neutral communities where symmetry is broken by a single species distinct from all others in ecological fitness and dispersal ability. In the latter case, our approximate distributions are fully normalized, and novel asymptotic expansions of the required hypergeometric functions are provided to make evaluations tractable for large communities. Employing these results in a bayesian analysis may provide a novel statistical test to assess the consistency of species abundance data with the neutral hypothesis. Copyright © 2010 Elsevier Ltd. All rights reserved.

  16. Catalytic Decoupling of Quantum Information

    DEFF Research Database (Denmark)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric


    The decoupling technique is a fundamental tool in quantum information theory with applications ranging from quantum thermodynamics to quantum many body physics to the study of black hole radiation. In this work we introduce the notion of catalytic decoupling, that is, decoupling in the presence...... of an uncorrelated ancilla system. This removes a restriction on the standard notion of decoupling, which becomes important for structureless resources, and yields a tight characterization in terms of the max-mutual information. Catalytic decoupling naturally unifies various tasks like the erasure of correlations...

  17. Theoretical insights into catalytic mechanism of protein arginine methyltransferase 1.

    Directory of Open Access Journals (Sweden)

    Ruihan Zhang

    Full Text Available Protein arginine methyltransferase 1 (PRMT1, the major arginine asymmetric dimethylation enzyme in mammals, is emerging as a potential drug target for cancer and cardiovascular disease. Understanding the catalytic mechanism of PRMT1 will facilitate inhibitor design. However, detailed mechanisms of the methyl transfer process and substrate deprotonation of PRMT1 remain unclear. In this study, we present a theoretical study on PRMT1 catalyzed arginine dimethylation by employing molecular dynamics (MD simulation and quantum mechanics/molecular mechanics (QM/MM calculation. Ternary complex models, composed of PRMT1, peptide substrate, and S-adenosyl-methionine (AdoMet as cofactor, were constructed and verified by 30-ns MD simulation. The snapshots selected from the MD trajectory were applied for the QM/MM calculation. The typical SN2-favored transition states of the first and second methyl transfers were identified from the potential energy profile. Deprotonation of substrate arginine occurs immediately after methyl transfer, and the carboxylate group of E144 acts as proton acceptor. Furthermore, natural bond orbital analysis and electrostatic potential calculation showed that E144 facilitates the charge redistribution during the reaction and reduces the energy barrier. In this study, we propose the detailed mechanism of PRMT1-catalyzed asymmetric dimethylation, which increases insight on the small-molecule effectors design, and enables further investigations into the physiological function of this family.

  18. Asymmetric packaging of polymerases within vesicular stomatitis virus

    Energy Technology Data Exchange (ETDEWEB)

    Hodges, Jeffery; Tang, Xiaolin; Landesman, Michael B. [Dept. of Physics and Astronomy, University of Utah (United States); Center for Cell and Genome Science, University of Utah (United States); Ruedas, John B. [Dept. of Biology, San Diego State University (United States); Ghimire, Anil [Dept. of Physics and Astronomy, University of Utah (United States); Gudheti, Manasa V. [Vutara, Inc., Salt Lake City, UT (United States); Dept. of Biology, University of Utah (United States); Perrault, Jacques [Dept. of Biology, San Diego State University (United States); Jorgensen, Erik M. [Howard Hughes Medical Institute (United States); Dept. of Biology, University of Utah (United States); Gerton, Jordan M. [Dept. of Physics and Astronomy, University of Utah (United States); Dept. of Bioengineering, University of Utah (United States); Saffarian, Saveez, E-mail: [Dept. of Physics and Astronomy, University of Utah (United States); Center for Cell and Genome Science, University of Utah (United States); Dept. of Biology, University of Utah (United States)


    Highlights: •The VSV polymerases (L proteins) are localized to the blunt end of the virus. •The VSV phosphoproteins (P proteins) are localized to the blunt end of the virus. •Each VSV virion packages a variable number of P and L proteins. -- Abstract: Vesicular stomatitis virus (VSV) is a prototypic negative sense single-stranded RNA virus. The bullet-shape appearance of the virion results from tightly wound helical turns of the nucleoprotein encapsidated RNA template (N-RNA) around a central cavity. Transcription and replication require polymerase complexes, which include a catalytic subunit L and a template-binding subunit P. L and P are inferred to be in the cavity, however lacking direct observation, their exact position has remained unclear. Using super-resolution fluorescence imaging and atomic force microscopy (AFM) on single VSV virions, we show that L and P are packaged asymmetrically towards the blunt end of the virus. The number of L and P proteins varies between individual virions and they occupy 57 ± 12 nm of the 150 nm central cavity of the virus. Our finding positions the polymerases at the opposite end of the genome with respect to the only transcriptional promoter.

  19. Asymmetric microscope. Fusho no kenbisho [exclamation point

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Tadashi. (Tokyo Institute of Technology, Tokyo (Japan))


    It is difficult for a conventional optical analysis means to determine the configuration of a substance with an ultra low optical purity. Recently, an asymmetric microscope has been reported as a new concept for solving the above-mentioned problem. Specifically, a product with slight asymmetry is obtained by using the substance with an ultra low optical purity as the chiral initiation, and then the asymmetry of the product is amplified dramatically due to the asymmetric autocatalysis, thus obtaining a product having a high optical purity. A new means is to determine the configuration of the original substance having the low optical purity from the configuration of the substance having the high optical purity. According to this method, the chirality of the substance having the low optical purity is transcribed to alkanol, and the chirality is amplified due to the asymmetric autocatalysis, thus the absolute configuration of the original compound can be determined from the absolute configuration of the final product. (NEDO)

  20. Multi-agent Bargaining under Asymmetric Information

    DEFF Research Database (Denmark)

    Asplund, Marcus; Genesove, David

    information aspect is due to partly unobserved individual valuations of an elevator. We tailor Hellwig (2003) to the features of the retrofitting problem and use this to predict which building characteristics should make it easier for owners to agree. Data from Copenhagen broadly support the model......It is well know that asymmetric information might lead to underprovision of public goods. To test the theoretical prediction, we study the decision to retrofit an elevator into an old apartment building, in which each owner has to agree on how the investment cost is split. The asymmetric......'s predictions. We use transaction data to estimate the market value of an elevator and conclude that for approximately 30-40 percent of the buildings without an elevator the aggregate increase in value exceeds the investment cost....

  1. Asymmetric synthesis II more methods and applications

    CERN Document Server

    Christmann, Mathias


    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...

  2. Asymmetric Catalysis with CO2 : The Direct α-Allylation of Ketones. (United States)

    Pupo, Gabriele; Properzi, Roberta; List, Benjamin


    Quaternary stereocenters are found in numerous bioactive molecules. The Tsuji-Trost reaction has proven to be a powerful C-C bond forming process, and, at least in principle, should be well suited to access quaternary stereocenters via the α-allylation of ketones. However, while indirect approaches are known, the direct, catalytic asymmetric α-allylation of branched ketones has been elusive until today. By combining "enol catalysis" with the use of CO2 as a formal catalyst for asymmetric catalysis, we have now developed a solution to this problem: we report a direct, highly enantioselective and highly atom-economic Tsuji-Trost allylation of branched ketones with allylic alcohol. Our reaction delivers products bearing quaternary stereocenters with high enantioselectivity and water as the sole by-product. We expect our methodology to be of utility in asymmetric catalysis and inspire the design of other highly atom-economic transformations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. A DFT based method for calculating the surface energies of asymmetric MoP facets (United States)

    Tian, Xinxin; Wang, Tao; Fan, Lifang; Wang, Yuekui; Lu, Haigang; Mu, Yuewen


    MoP is a promising catalyst in heterogeneous catalysis. Understanding its surface stability and morphology is the first and essential step in exploring its catalytic properties. However, traditional surface energy calculation method does not work for the asymmetric termination of MoP. In this work, we reported a useful DFT based method to get the surface energies of asymmetric MoP facets. Under ideal condition, the (101) surface with mixed Mo/P termination is most stable, followed by the (100) surface, while the (001) surface is least stable. Wulff construction reveals the exposure of six surfaces on the MoP nanoparticle, where the (101) has the largest contribution. Atomistic thermodynamics results reveal the changes in surface stability orders with experimental conditions, and the (001)-P termination becomes more and more stable with increasing P chemical potential, which indicates its exposure is possible at defined conditions. Our results agree well with the previous experimental XRD and TEM data. We believe the reported method for surface energy calculation could be extended to other similar systems with asymmetric surface terminations.

  4. Non-stabilized nucleophiles in Cu-catalysed dynamic kinetic asymmetric allylic alkylation (United States)

    You, Hengzhi; Rideau, Emeline; Sidera, Mireia; Fletcher, Stephen P.


    The development of new reactions forming asymmetric carbon-carbon bonds has enabled chemists to synthesize a broad range of important carbon-containing molecules, including pharmaceutical agents, fragrances and polymers. Most strategies to obtain enantiomerically enriched molecules rely on either generating new stereogenic centres from prochiral substrates or resolving racemic mixtures of enantiomers. An alternative strategy--dynamic kinetic asymmetric transformation--involves the transformation of a racemic starting material into a single enantiomer product, with greater than 50 per cent maximum yield. The use of stabilized nucleophiles (pKa =50, more than 25 orders of magnitude more basic than the nucleophiles that are typically used in such transformations. Organometallic reagents are generated in situ from alkenes by hydrometallation and give highly enantioenriched products under mild reaction conditions. The method is used to synthesize natural products that possess activity against tuberculosis and leprosy, and an inhibitor of para-aminobenzoate biosynthesis. Mechanistic studies indicate that the reaction proceeds through a rapidly isomerizing intermediate. We anticipate that this approach will be a valuable complement to existing asymmetric catalytic methods.

  5. Nucleophilic addition to an achiral dehydroalanine Schiff base Ni(II) complex as a route to amino acids. A case of stereodetermining asymmetric protonation in the presence of TADDOL

    NARCIS (Netherlands)

    Belokon, Yuri N.; Harutyunyan, Syuzanna; Vorontsov, Evgeni V.; Peregudov, Alexander S.; Chrustalev, Viktor N.; Kochetkov, Konstantin A.; Pripadchev, Dmitriy; Sagyan, Ashot S.; Beck, Albert K.; Seebach, Dieter


    We describe herein the elaboration of a new type of a substrate based on the Ni(II) complex of a Schiff base of dehydroalanine, 1, and Michael addition of nucleophiles to it, leading to the synthesis of racemic α-amino acids. We have also developed a catalytic method for the asymmetric 1,4 conjugate

  6. Catalytic carboxyester hydrolysis by diaminodiphenols

    Indian Academy of Sciences (India)


    Two diaminodiphenols, 1 and 2, have been examined as catalysts for the hydrolysis of 4- nitrophenyl acetate (NA) and 4-nitrophenylphosphate (NP) in aqueous-acetonitrile (25% acetonitrile v/v) media at 35ºC, I = 1·0 mol dm–3. The compound 1 enhances the hydrolysis rate of NA more than 105 times. Its catalytic efficiency ...

  7. Self-Moving Catalytic Nanomotors (United States)


    substrate turnover. (c) The identification of a new mechanism for producing self-generated flows. This involves auto diffusio- osmosis due to the...speed (and thus apparent diffusivity on a longer timescale) increases with increasing substrate concentration. More interestingly, the motors were...motors fabricated by the attachment of Grubbs’ catalyst asymmetrically to gold-silica Janus microspheres. These motors show increased diffusion when

  8. Algebraic Davis decomposition and asymmetric Doob inequalities


    Hong, Guixiang; Junge, Marius; Parcet, Javier


    In this paper we investigate asymmetric forms of Doob maximal inequality. The asymmetry is imposed by noncommutativity. Let $(\\M,\\tau)$ be a noncommutative probability space equipped with a weak-$*$ dense filtration of von Neumann subalgebras $(\\M_n)_{n \\ge 1}$. Let $\\E_n$ denote the corresponding family of conditional expectations. As an illustration for an asymmetric result, we prove that for $1 < p < 2$ and $x \\in L_p(\\M,\\tau)$ one can find $a, b \\in L_p(\\M,\\tau)$ and contractions $u_n, v_...

  9. Asymmetric multiscale behavior in PM2.5 time series: Based on asymmetric MS-DFA (United States)

    Zhang, Chen; Ni, Zhiwei; Ni, Liping


    Particulate matter with an aerodynamic diameter of 2.5 mm or less (PM2.5) is one of the most serious air pollution, considered most harmful for people by World Health Organisation. In this paper, we utilized the asymmetric multiscale detrended fluctuation analysis (A-MSDFA) method to explore the existence of asymmetric correlation properties for PM2.5 daily average concentration in two USA cities (Fresno and Los Angeles) and two Chinese cities (Hong Kong and Shanghai), and to assess the properties of these asymmetric correlations. The results show the existences of asymmetric correlations, and the degree of asymmetric for two USA cities is stronger than that of two Chinese cities. Further, most of the local exponent β(n) are smaller than 0.5, which indicates the existence of anti-persistent long-range correlation for PM2.5 time series in four cities. In addition, we reanalyze the asymmetric correlation by the A-MSDFA method with secant rolling windows of different sizes, which can investigate dynamic changes in the multiscale correlation for PM2.5 time series with changing window size. Whatever window sizes, the correlations are asymmetric and display smaller asymmetries at small scales and larger asymmetries at large scales. Moreover, the asymmetries become increasingly weaker with the increase of window sizes.

  10. Cell-sized asymmetric lipid vesicles facilitate the investigation of asymmetric membranes (United States)

    Kamiya, Koki; Kawano, Ryuji; Osaki, Toshihisa; Akiyoshi, Kazunari; Takeuchi, Shoji


    Asymmetric lipid giant vesicles have been used to model the biochemical reactions in cell membranes. However, methods for producing asymmetric giant vesicles lead to the inclusion of an organic solvent layer that affects the mechanical and physical characteristics of the membrane. Here we describe the formation of asymmetric giant vesicles that include little organic solvent, and use them to investigate the dynamic responses of lipid molecules in the vesicle membrane. We formed the giant vesicles via the inhomogeneous break-up of a lipid microtube generated by applying a jet flow to an asymmetric planar lipid bilayer. The asymmetric giant vesicles showed a lipid flip-flop behaviour in the membrane, superficially similar to the lipid flip-flop activity observed in apoptotic cells. In vitro synthesis of membrane proteins into the asymmetric giant vesicles revealed that the lipid asymmetry in bilayer membranes improves the reconstitution ratio of membrane proteins. Our asymmetric giant vesicles will be useful in elucidating lipid-lipid and lipid-membrane protein interactions involved in the regulation of cellular functions.

  11. RSA Asymmetric Cryptosystem beyond Homogeneous Transformation

    African Journals Online (AJOL)



    Dec 1, 2013 ... The Internet is an insecure open network and its use and connectivity have witnessed a significant growth, and this has made it vulnerable to all forms of attacks. A threat to a network can cause harm or interrupt the network. In this paper, we looked at the security of data and message, using asymmetric.

  12. Settling dynamics of asymmetric rigid fibers (United States)

    E.J. Tozzi; C Tim Scott; David Vahey; D.J. Klingenberg


    The three-dimensional motion of asymmetric rigid fibers settling under gravity in a quiescent fluid was experimentally measured using a pair of cameras located on a movable platform. The particle motion typically consisted of an initial transient after which the particle approached a steady rate of rotation about an axis parallel to the acceleration of gravity, with...

  13. Computing modal dispersion characteristics of radially Asymmetric ...

    African Journals Online (AJOL)

    determine how the modal characteristics change as circular Bragg fiber is changed to asymmetric Bragg fiber. The key to this transfer matrix method (TMM) is the accurate calculation of the propagation constants of modes. And validity of this method is verified by FDTD method. We compare these results with obtained from ...

  14. Organocatalytic asymmetric transfer hydrogenation of imines

    NARCIS (Netherlands)

    de Vries, Johannes G.; Mrsic, Natasa; Mršić, Nataša


    The asymmetric organocatalytic transfer hydrogenation of imines can be accomplished in good yields with high enantioselectivities through the use of BINOL-derived phosphoric acids as catalysts and Hantzsch esters or benzothiazoles as the hydride source. The same method can also be applied to the

  15. Spatially inhomogeneous condensate in asymmetric nuclear matter

    NARCIS (Netherlands)

    Sedrakian, A

    We study the isospin singlet pairing in asymmetric nuclear matter with nonzero total momentum of the condensate Cooper pairs. The quasiparticle excitation spectrum is fourfold split compared to the usual BCS spectrum of the symmetric, homogeneous matter. A twofold splitting of the spectrum into

  16. Asymmetric volatility connectedness on the forex market

    Czech Academy of Sciences Publication Activity Database

    Baruník, Jozef; Kočenda, Evžen; Vácha, Lukáš


    Roč. 77, č. 1 (2017), s. 39-56 ISSN 0261-5606 R&D Projects: GA ČR(CZ) GA16-14179S Institutional support: RVO:67985556 Keywords : volatility * connectedness * asymmetric effects Subject RIV: AH - Economics Impact factor: 1.853, year: 2016 http:// library

  17. Asymmetric Drift and the Stellar Velocity Ellipsoid

    NARCIS (Netherlands)

    Westfall, Kyle B.; Bershady, Matthew A.; Verheijen, Marc A. W.; Andersen, David R.; Swaters, Rob A.


    We present the decomposition of the stellar velocity ellipsoid using stellar velocity dispersions within a 40° wedge about the major-axis (smaj), the epicycle approximation, and the asymmetric drift equation. Thus, we employ no fitted forms for smaj and escape interpolation errors resulting from

  18. Dynamic Conditional Correlations for Asymmetric Processes

    NARCIS (Netherlands)

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


    textabstractThe paper develops two Dynamic Conditional Correlation (DCC) models, namely the Wishart DCC (WDCC) model and the Matrix-Exponential Conditional Correlation (MECC) model. The paper applies the WDCC approach to the exponential GARCH (EGARCH) and GJR models to propose asymmetric DCC models.

  19. Asymmetric conditional volatility in international stock markets (United States)

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


    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.

  20. Spectral inequalities for the quantum asymmetric top

    Energy Technology Data Exchange (ETDEWEB)

    Bourget, Alain; McMillen, Tyler [Department of Mathematics, California State University (Fullerton), McCarthy Hall 154, Fullerton, CA 92834 (United States)], E-mail:, E-mail:


    We consider the spectrum of the quantum asymmetric top. Unlike in the case when two or three moments of inertia are equal, when the moments of inertia are distinct all degeneracy in the spectrum of the operator is removed. We derive inequalities for the spectra based on recent results on the interlacing of Van Vleck zeros.

  1. Palladium catalysed asymmetric alkylation of benzophenone Schiff ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 4. Palladium catalysed asymmetric alkylation of benzophenone Schiff base glycine esters in ionic liquids. Dae Hyun Kim Jin Kyu Im Dae Won Kim Minserk Cheong Hoon Sik Kim Deb Kumar Mukherjee. Volume 123 Issue 4 July 2011 pp 467-476 ...

  2. RSA Asymmetric Cryptosystem beyond Homogeneous Transformation

    African Journals Online (AJOL)

    The Internet is an insecure open network and its use and connectivity have witnessed a significant growth, and this has made it vulnerable to all forms of attacks. A threat to a network can cause harm or interrupt the network. In this paper, we looked at the security of data and message, using asymmetric cryptography, with ...

  3. Mixed gas plasticization phenomena in asymmetric membranes

    NARCIS (Netherlands)

    Visser, Tymen


    This thesis describes the thorough investigation of mixed gas transport behavior of asymmetric membranes in the separation of feed streams containing plasticizing gases in order to gain more insights into the complicated behavior of plasticization. To successfully employ gas separation membranes in

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

    DEFF Research Database (Denmark)

    Masina, Isabella; Sannino, Francesco


    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....

  5. Determinant of asymmetric risks in Nigerian loan market: any ...

    African Journals Online (AJOL)

    Bank lending in Nigeria was dominated by the presence of asymmetric information, a wedge to financial intermediation. Using probit and correlation test methodology, evidence of low level asymmetric risk was found and the determinants of asymmetric risks in the market were not significantly different. The size of default ...

  6. Catalytic Fast Pyrolysis: A Review

    Directory of Open Access Journals (Sweden)

    Theodore Dickerson


    Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

  7. Catalytic combustion of residual fuels (United States)

    Bulzan, D. L.; Tacina, R. R.


    A noble metal catalytic reactor was tested using two grades of petroleum derived residual fuels at specified inlet air temperatures, pressures, and reference velocities. Combustion efficiencies greater than 99.5 percent were obtained. Steady state operation of the catalytic reactor required inlet air temperatures of at least 800 K. At lower inlet air temperatures, upstream burning in the premixing zone occurred which was probably caused by fuel deposition and accumulation on the premixing zone walls. Increasing the inlet air temperature prevented this occurrence. Both residual fuels contained about 0.5 percent nitrogen by weight. NO sub x emissions ranged from 50 to 110 ppm by volume at 15 percent excess O2. Conversion of fuel-bound nitrogen to NO sub x ranged from 25 to 50 percent.

  8. Catalytic electrochemistry of xanthine dehydrogenase. (United States)

    Kalimuthu, Palraj; Leimkühler, Silke; Bernhardt, Paul V


    We report the mediated electrocatalytic voltammetry of the molybdoenzyme xanthine dehydrogenase (XDH) from Rhodobacter capsulatus at a thiol-modified Au electrode. The 2-electron acceptor N-methylphenazinium methanesulfonate (phenazine methosulfate, PMS) is an effective artificial electron transfer partner for XDH instead of its native electron acceptor NAD(+). XDH catalyzes the oxidative hydroxylation of hypoxanthine to xanthine and xanthine to uric acid. Cyclic voltammetry was used to generate the active (oxidized) form of the mediator. Simulation of the catalytic voltammetry across a broad range of substrate and PMS concentrations at different sweep rates was achieved with the program DigiSim to yield a set of consistent rate and equilibrium constants that describe the catalytic system. This provides the first example of the mediated electrochemistry of a xanthine dehydrogenase (or oxidase) that is uncomplicated by interference from product oxidation. A remarkable two-step, sequential oxidation of hypoxanthine to uric acid via xanthine by XDH is observed.

  9. Crystallization and preliminary crystallographic studies of the Pasteurella multocida toxin catalytic domain. (United States)

    Miyazawa, Masayuki; Kitadokoro, Kengo; Kamitani, Shigeki; Shime, Hiroaki; Horiguchi, Yasuhiko


    The C-terminal catalytic domain of Pasteurella multocida toxin, which is the virulence factor of the organism in P. multocida, has been expressed, purified and subsequently crystallized using the sitting-drop vapour-diffusion technique. Native diffraction data to 1.9 A resolution were obtained at the BL44XU beamline of SPring-8 from a flash-frozen crystal at 100 K. The crystals belong to space group C2, with unit-cell parameters a = 111.0, b = 150.4, c = 77.1 A, beta = 105.5 degrees, and are likely to contain one C-PMT (726 residues) per asymmetric unit.

  10. Sixteen isostructural phosphonate metal-organic frameworks with controlled Lewis acidity and chemical stability for asymmetric catalysis. (United States)

    Chen, Xu; Peng, Yongwu; Han, Xing; Liu, Yan; Lin, Xiaochao; Cui, Yong


    Heterogeneous catalysts typically lack the specific steric control and rational electronic tuning required for precise asymmetric catalysis. Here we demonstrate that a phosphonate metal-organic framework (MOF) platform that is robust enough to accommodate up to 16 different metal clusters, allowing for systematic tuning of Lewis acidity, catalytic activity and enantioselectivity. A total of 16 chiral porous MOFs, with the framework formula [M3 L 2(solvent)2] that have the same channel structures but different surface-isolated Lewis acid metal sites, are prepared from a single phosphono-carboxylate ligand of 1,1'-biphenol and 16 different metal ions. The phosphonate MOFs possessing tert-butyl-coated channels exhibited high thermal stability and good tolerances to boiling water, weak acid and base. The MOFs provide a versatile family of heterogeneous catalysts for asymmetric allylboration, propargylation, Friedel-Crafts alkylation and sulfoxidation with good to high enantioselectivity. In contrast, the homogeneous catalyst systems cannot catalyze the test reactions enantioselectively.

  11. 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)


    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.

  12. Block copolymer hollow fiber membranes with catalytic activity and pH-response

    KAUST Repository

    Hilke, Roland


    We fabricated block copolymer hollow fiber membranes with self-assembled, shell-side, uniform pore structures. The fibers in these membranes combined pores able to respond to pH and acting as chemical gates that opened above pH 4, and catalytic activity, achieved by the incorporation of gold nanoparticles. We used a dry/wet spinning process to produce the asymmetric hollow fibers and determined the conditions under which the hollow fibers were optimized to create the desired pore morphology and the necessary mechanical stability. To induce ordered micelle assembly in the doped solution, we identified an ideal solvent mixture as confirmed by small-angle X-ray scattering. We then reduced p-nitrophenol with a gold-loaded fiber to confirm the catalytic performance of the membranes. © 2013 American Chemical Society.

  13. Crystallization and preliminary crystallographic studies of the Pasteurella multocida toxin catalytic domain

    Energy Technology Data Exchange (ETDEWEB)

    Miyazawa, Masayuki [Research Institute for Microbial Diseases, Osaka University, 3-1 Yamada-oka, Suita-shi, Osaka 565-0871 (Japan); Kitadokoro, Kengo [Research Center for Low Temperature and Materials Sciences, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan); Kamitani, Shigeki; Shime, Hiroaki; Horiguchi, Yasuhiko, E-mail: [Research Institute for Microbial Diseases, Osaka University, 3-1 Yamada-oka, Suita-shi, Osaka 565-0871 (Japan)


    The C-terminal catalytic domain of P. multocida toxin, which is the virulence factor of the organism in P. multocida, has been expressed, purified and subsequently crystallized using the sitting-drop vapour-diffusion technique. The C-terminal catalytic domain of Pasteurella multocida toxin, which is the virulence factor of the organism in P. multocida, has been expressed, purified and subsequently crystallized using the sitting-drop vapour-diffusion technique. Native diffraction data to 1.9 Å resolution were obtained at the BL44XU beamline of SPring-8 from a flash-frozen crystal at 100 K. The crystals belong to space group C2, with unit-cell parameters a = 111.0, b = 150.4, c = 77.1 Å, β = 105.5°, and are likely to contain one C-PMT (726 residues) per asymmetric unit.

  14. High average power scaleable thin-disk laser (United States)

    Beach, Raymond J.; Honea, Eric C.; Bibeau, Camille; Payne, Stephen A.; Powell, Howard; Krupke, William F.; Sutton, Steven B.


    Using a thin disk laser gain element with an undoped cap layer enables the scaling of lasers to extremely high average output power values. Ordinarily, the power scaling of such thin disk lasers is limited by the deleterious effects of amplified spontaneous emission. By using an undoped cap layer diffusion bonded to the thin disk, the onset of amplified spontaneous emission does not occur as readily as if no cap layer is used, and much larger transverse thin disks can be effectively used as laser gain elements. This invention can be used as a high average power laser for material processing applications as well as for weapon and air defense applications.

  15. Preparation of Mesoporous SBA-16 Silica-Supported Biscinchona Alkaloid Ligand for the Asymmetric Dihydroxylation of Olefins

    Directory of Open Access Journals (Sweden)

    Shaheen M. Sarkar


    Full Text Available Optically active cinchona alkaloid was anchored onto mesoporous SBA-16 silica and the as-prepared complex was used as a heterogeneous chiral ligand of osmium tetraoxide for the asymmetric dihydroxylation of olefins. The prepared catalytic system provided 90–93% yield of vicinal diol with 92–99% enantioselectivity. The ordered mesoporous SBA-16 silica was found to be a valuable support for the cinchona alkaloid liganded osmium catalyst system which is frequently used in chemical industries and research laboratories for olefin functionalization.

  16. Asymmetric Electrophilic Fluorination of β-Keto Phosphonates in Ionic Liquid Media Catalyzed by Chiral Palladium Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung Min; Kang, Young Ku; Mang, Joo Yang; Kim, Dae Young [Soonchunhyang University, Asan (Korea, Republic of); Lee, Kil Sung [Cheil Industries Inc., Euiwang, (Korea, Republic of)


    We have accomplished the highly efficient catalytic enantioselective fluorination of β-keto phosphonates with excellent yield and enantioselectivity in ionic liquid, which simplify product isolation and catalyst recycling. The chemistry of bioactive organofluorine compounds is a rapidly developing area of research because of their importance in biochemical and medicinal application. Chiral organofluorine compounds containing a fluorine atom bonded directly to a stereogenic center have been utilized in studies of enzyme mechanisms and as intermediates in asymmetric syntheses. The development of effective methodologies for the preparation of new selectively fluorinated, stereochemically defined compounds is critical to further advances of fluorine chemistry. The catalytic enantioselective construction of fluorinated stereogenic centers is still important challenge in modern organic chemistry.

  17. Settling dynamics of asymmetric rigid fibers (United States)

    Tozzi, E. J.; Scott, C. T.; Vahey, D.; Klingenberg, D. J.


    The three-dimensional motion of asymmetric rigid fibers settling under gravity in a quiescent fluid was experimentally measured using a pair of cameras located on a movable platform. The particle motion typically consisted of an initial transient after which the particle approached a steady rate of rotation about an axis parallel to the acceleration of gravity, with its center of mass following a helical trajectory. Numerical and analytical methods were used to predict translational and angular velocities as well as the evolution of the fiber orientation as a function of time. A comparison of calculated and measured values shows that it is possible to quantitatively predict complex motions of particles that have highly asymmetric shape. The relations between particle shape and settling trajectory have potential applications for hydrodynamic characterization of fiber shapes and fiber separation.

  18. Enhancing molecule fluorescence with asymmetrical plasmonic antennas. (United States)

    Lu, Guowei; Liu, Jie; Zhang, Tianyue; Shen, Hongming; Perriat, Pascal; Martini, Matteo; Tillement, Olivier; Gu, Ying; He, Yingbo; Wang, Yuwei; Gong, Qihuang


    We propose and justify by the finite-difference time-domain method an efficient strategy to enhance the spontaneous emission of a fluorophore with a multi-resonance plasmonic antenna. The custom-designed asymmetrical antenna consists of two plasmonic nanoparticles with different sizes and is able to couple efficiently to free space light through multiple localized surface plasmon resonances. This design simultaneously permits a large near-field excitation near the antenna as well as a high quantum efficiency, which results in an unusual and significant enhancement of the fluorescence of a single emitter. Such an asymmetrical antenna presents intrinsic advantages over single particle or dimer based antennas made using two identical nanostructures. This promising concept can be exploited in the large domain of light-matter interaction processes involving multiple frequencies.

  19. Defect induced asymmetric pit formation on hydroxyapatite. (United States)

    Kwon, Ki-Young; Wang, Eddie; Chung, Alice; Chang, Neil; Saiz, Eduardo; Choe, Uh-Joo; Koobatian, Maxwell; Lee, Seung-Wuk


    Defect sites on bone minerals play a critical role in bone remodeling processes. We investigated single crystal hydroxyapatite (100) surfaces bearing crystal defects under acidic dissolution conditions using real-time in situ atomic force microscopy. At defect sites, surface structure-dependent asymmetric hexagonal etch pits were formed, which dominated the overall dissolution rate. Meanwhile, dissolution from the flat terraces proceeded by stochastic formation of flat bottom etch pits. The resulting pit shapes were intrinsically dictated by the HAP crystal structure. Computational modeling also predicted different step energies associated with different facets of the asymmetric etch pits. Our microscopic observations of HAP dissolution are significant for understanding the effects of local surface structure on the bone mineral remodeling process and provide useful insights for the design of novel therapies for treating osteoporosis and dental caries.

  20. Asymmetric synthesis and sensory evaluation of sedanenolide. (United States)

    Oguro, Daichi; Watanabe, Hidenori


    The synthesis and sensory evaluation of enantiomeric sets of sedanenolide (1) and 3-butylphthalide (3) are described. The asymmetric synthesis was achieved via the intramolecular Diels-Alder reaction of chiral propargylester (5) which was prepared from optically active propargyl alcohol (4) and 2,4-pentadienoic acid. The sensory evaluation of these enantiomers revealed that there were distinct differences between their aroma character and odor threshold.

  1. Asymmetric k-Center with Minimum Coverage

    DEFF Research Database (Denmark)

    Gørtz, Inge Li


    In this paper we give approximation algorithms and inapproximability results for various asymmetric k-center with minimum coverage problems. In the k-center with minimum coverage problem, each center is required to serve a minimum number of clients. These problems have been studied by Lim et al. [A....... Lim, B. Rodrigues, F. Wang, Z. Xu, k-center problems with minimum coverage, Theoret. Comput. Sci. 332 (1–3) (2005) 1–17] in the symmetric setting....

  2. Asymmetric monetary policy effects in EMU


    Clausen, Volker; Hayo, Bernd


    This paper uses a semi-structural dynamic modelling approach to investigate asymmetric monetary transmission in Europe. A system of equations containing reaction functions for monetary policy, output and inflation equations is simultaneously estimated for France, Germany, and Italy. Extensive cross equation tests show that relatively large differences in simulated impulse responses are still consistent with the notion that the transmission mechanism is homogeneous across the three major EMU c...

  3. Predicting tensorial electrophoretic effects in asymmetric colloids (United States)

    Mowitz, Aaron J.; Witten, T. A.


    We formulate a numerical method for predicting the tensorial linear response of a rigid, asymmetrically charged body to an applied electric field. This prediction requires calculating the response of the fluid to the Stokes drag forces on the moving body and on the countercharges near its surface. To determine the fluid's motion, we represent both the body and the countercharges using many point sources of drag known as Stokeslets. Finding the correct flow field amounts to finding the set of drag forces on the Stokeslets that is consistent with the relative velocities experienced by each Stokeslet. The method rigorously satisfies the condition that the object moves with no transfer of momentum to the fluid. We demonstrate that a sphere represented by 1999 well-separated Stokeslets on its surface produces flow and drag force like a solid sphere to 1% accuracy. We show that a uniformly charged sphere with 3998 body and countercharge Stokeslets obeys the Smoluchowski prediction [F. Morrison, J. Colloid Interface Sci. 34, 210 (1970), 10.1016/0021-9797(70)90171-2] for electrophoretic mobility when the countercharges lie close to the sphere. Spheres with dipolar and quadrupolar charge distributions rotate and translate as predicted analytically to 4% accuracy or better. We describe how the method can treat general asymmetric shapes and charge distributions. This method offers promise as a way to characterize and manipulate asymmetrically charged colloid-scale objects from biology (e.g., viruses) and technology (e.g., self-assembled clusters).

  4. Asymmetric threat data mining and knowledge discovery (United States)

    Gilmore, John F.; Pagels, Michael A.; Palk, Justin


    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.

  5. Dynamic Responsive Systems for Catalytic Function. (United States)

    Vlatković, Matea; Collins, Beatrice S L; Feringa, Ben L


    Responsive systems have recently gained much interest in the scientific community in attempts to mimic dynamic functions in biological systems. One of the fascinating potential applications of responsive systems lies in catalysis. Inspired by nature, novel responsive catalytic systems have been built that show analogy with allosteric regulation of enzymes. The design of responsive catalytic systems allows control of catalytic activity and selectivity. In this Review, advances in the field over the last four decades are discussed and a comparison is made amongst the dynamic responsive systems based on the principles underlying their catalytic mechanisms. The catalyst systems are sorted according to the triggers used to achieve control of the catalytic activity and the distinct catalytic reactions illustrated. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel


    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  7. Catalytic Decoupling of Quantum Information. (United States)

    Majenz, Christian; Berta, Mario; Dupuis, Frédéric; Renner, Renato; Christandl, Matthias


    The decoupling technique is a fundamental tool in quantum information theory with applications ranging from thermodynamics to many-body physics and black hole radiation whereby a quantum system is decoupled from another one by discarding an appropriately chosen part of it. Here, we introduce catalytic decoupling, i.e., decoupling with the help of an independent system. Thereby, we remove a restriction on the standard decoupling notion and present a tight characterization in terms of the max-mutual information. The novel notion unifies various tasks and leads to a resource theory of decoupling.

  8. Molecular catalytic coal liquid conversion

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.; Yang, Shiyong [Univ. of Chicago, IL (United States)


    This research, which is relevant to the development of new catalytic systems for the improvement of the quality of coal liquids by the addition of dihydrogen, is divided into two tasks. Task 1 centers on the activation of dihydrogen by molecular basic reagents such as hydroxide ion to convert it into a reactive adduct (OH{center_dot}H{sub 2}){sup {minus}} that can reduce organic molecules. Such species should be robust withstanding severe conditions and chemical poisons. Task 2 is focused on an entirely different approach that exploits molecular catalysts, derived from organometallic compounds that are capable of reducing monocyclic aromatic compounds under very mild conditions. Accomplishments and conclusions are discussed.

  9. Catalytic Combustion of Ethyl Acetate


    ÖZÇELİK, Tuğba GÜRMEN; ATALAY, Süheyda; ALPAY, Erden


    The catalytic combustion of ethyl acetate over prepared metal oxide catalysts was investigated. CeO, Co2O3, Mn2O3, Cr2O3, and CeO-Co2O3 catalysts were prepared on monolith supports and they were tested. Before conducting the catalyst experiments, we searched for the homogeneous gas phase combustion reaction of ethyl acetate. According to the homogeneous phase experimental results, 45% of ethyl acetate was converted at the maximum reactor temperature tested (350 °C). All the prepare...

  10. Computational Introduction of Catalytic Activity into Proteins. (United States)

    Bertolani, Steve J; Carlin, Dylan Alexander; Siegel, Justin B


    Recently, there have been several successful cases of introducing catalytic activity into proteins. One method that has been used successfully to achieve this is the theozyme placement and enzyme design algorithms implemented in Rosetta Molecular Modeling Suite. Here, we illustrate how to use this software to recapitulate the placement of catalytic residues and ligand into a protein using a theozyme, protein scaffold, and catalytic constraints as input.

  11. Asymmetrical lumbosacral transitional vertebrae in dogs may promote asymmetrical hip joint development. (United States)

    Flückiger, Mark A; Steffen, Frank; Hässig, Michael; Morgan, Joseph P


    This study examines the relationship between the morphology of the lumbosacral transitional vertebra (LTV) and asymmetrical development of the hip joints in dogs. A total of 4000 dogs which had been consecutively scored for canine hip dysplasia were checked for the presence of a LTV. A LTV was noted in 138 dogs and classified depending on the morphology of the transverse processes and the degree of contact with the ilium. In dogs with an asymmetrical LTV, the hip joint was significantly more predisposed to subluxation and malformation on the side of the intermediate or sacral-like transverse process (p hip joint conformation was less affected on the side featuring a free transverse process (p hip joint, and secondary osteoarthritis. Asymmetrical hip conformation may therefore be the sequela of a LTV and mask or aggravate genetically induced canine hip dysplasia.

  12. Nanostructured Catalytic Reactors for Air Purification Project (United States)

    National Aeronautics and Space Administration — This SBIR Phase I project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  13. Nanostructured Catalytic Reactors for Air Purification Project (United States)

    National Aeronautics and Space Administration — This SBIR Phase II project proposes the development of lightweight compact nanostructured catalytic reactors for air purification from toxic gaseous organic...

  14. Catalytic enantioselective Reformatsky reaction with ketones

    NARCIS (Netherlands)

    Fernandez-Ibanez, M. Angeles; Macia, Beatriz; Minnaard, Adriaan J.; Feringa, Ben L.


    Chiral tertiary alcohols were obtained with good yields and enantioselectivities via a catalytic Reformatsky reaction with ketones, including the challenging diaryl ketones, using chiral BINOL derivatives.

  15. Asymmetric Cycloaddition and Cyclization Reactions Catalyzed by Chiral N,N'-Dioxide-Metal Complexes. (United States)

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


    Catalytic asymmetric cycloadditions and cascade cyclizations are a major focus for the enantioselective construction of chiral carbo- and heterocycles. A number of chiral Lewis acids and organocatalysts have been designed for such reactions. The development of broadly applicable catalysts bearing novel chiral backbones to meet the demands of various applications is an ongoing challenge. Approximately 10 years ago, we introduced a group of conformationally flexible C2-symmetric N,N'-dioxide amide compounds, which represent a new class of privileged ligands. The coordination of the four oxygens of a chiral N,N'-dioxide around a central metal generates an octahedral tricyclometalated Lewis acid catalyst that can carry out various enantioselective reactions. In this Account, we summarize our recent studies on asymmetric cycloadditions between various dienophiles and dienes, dipoles and dipolarophiles, and cascade cyclizations catalyzed by chiral N,N'-dioxide-metal complexes. In principle, these unique chiral catalysts lower the LUMO energy of electron-deficient 2π components or heterodienes by coordination with the functional groups via various binding modes. With N-Boc-3-alkenyloxindole and alkylidene malonate as the electron-deficient 2π components, N,N'-dioxide-metal complexes provided excellent catalytic activities and asymmetric inductions for a variety of transformations, including [2 + 1], [3 + 2], [4 + 2], and [8 + 2] cycloadditions. Mechanistically, these substrates could be efficiently activated through bidentate coordination. The strategy was also useful for asymmetric cascade cyclizations to form polycyclic adducts. Monodentate or bidentate coordination of other α,β-unsubstituted carbonyl compounds to metal centers enabled both normal Diels-Alder reactions and inverse-electron-demand hetero-Diels-Alder reactions as well as [2 + 2] additions. Furthermore, hetero-Diels-Alder reactions of aldehydes, ketones, and imines are well-tolerated and afford various

  16. Biocatalytic asymmetric synthesis of chiral amines from ketones applied to sitagliptin manufacture. (United States)

    Savile, Christopher K; Janey, Jacob M; Mundorff, Emily C; Moore, Jeffrey C; Tam, Sarena; Jarvis, William R; Colbeck, Jeffrey C; Krebber, Anke; Fleitz, Fred J; Brands, Jos; Devine, Paul N; Huisman, Gjalt W; Hughes, Gregory J


    Pharmaceutical synthesis can benefit greatly from the selectivity gains associated with enzymatic catalysis. Here, we report an efficient biocatalytic process to replace a recently implemented rhodium-catalyzed asymmetric enamine hydrogenation for the large-scale manufacture of the antidiabetic compound sitagliptin. Starting from an enzyme that had the catalytic machinery to perform the desired chemistry but lacked any activity toward the prositagliptin ketone, we applied a substrate walking, modeling, and mutation approach to create a transaminase with marginal activity for the synthesis of the chiral amine; this variant was then further engineered via directed evolution for practical application in a manufacturing setting. The resultant biocatalysts showed broad applicability toward the synthesis of chiral amines that previously were accessible only via resolution. This work underscores the maturation of biocatalysis to enable efficient, economical, and environmentally benign processes for the manufacture of pharmaceuticals.

  17. Multicatalytic, asymmetric Michael/Stetter reaction of salicylaldehydes and activated alkynes (United States)

    Filloux, Claire M.; Lathrop, Stephen P.; Rovis, Tomislav


    We report the development of a multicatalytic, one-pot, asymmetric Michael/Stetter reaction between salicylaldehydes and electron-deficient alkynes. The cascade proceeds via amine-mediated Michael addition followed by an N-heterocyclic carbene-promoted intramolecular Stetter reaction. A variety of salicylaldehydes, doubly activated alkynes, and terminal, electrophilic allenes participate in a one-step or two-step protocol to give a variety of benzofuranone products in moderate to good yields and good to excellent enantioselectivities. The origin of enantioselectivity in the reaction is also explored; E/Z geometry of the reaction intermediate as well as the presence of catalytic amounts of catechol additive are found to influence reaction enantioselectivity. PMID:20639467

  18. Asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with a new trifluoromethoxylation reagent (United States)

    Guo, Shuo; Cong, Fei; Guo, Rui; Wang, Liang; Tang, Pingping


    Fluorinated organic compounds are becoming increasingly important in pharmaceuticals, agrochemicals and materials science. The introduction of trifluoromethoxy groups into new drugs and agrochemicals has attracted much attention due to their strongly electron-withdrawing nature and high lipophilicity. However, synthesis of trifluoromethoxylated organic molecules is difficult owing to the decomposition of trifluoromethoxide anion and β-fluoride elimination from transition-metal-trifluoromethoxide complexes, and no catalytic enantioselective trifluoromethoxylation reaction has been reported until now. Here, we present an example of an asymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with trifluoromethyl arylsulfonate (TFMS) as a new trifluoromethoxylation reagent. Compared to other trifluoromethoxylation reagents, TFMS is easily prepared and thermally stable with good reactivity. In addition, this reaction is operationally simple, scalable and proceeds under mild reaction conditions. Furthermore, broad scope and good functional group compatibility has been demonstrated by application of the method to the bromotrifluoromethoxylation of double bonds in natural products and natural product derivatives.

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


    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.

  20. Catalytic conversion of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Lyons, J.E.


    The second Quarterly Report of 1992 on the Catalytic Conversion of Light Alkanes reviews the work done between April 1, 1992 and June 31, 1992 on the Cooperative Agreement. The mission of this work is to devise a new catalyst which can be used in a simple economic process to convert the light alkanes in natural gas to oxygenate products that can either be used as clean-burning, high octane liquid fuels, as fuel components or as precursors to liquid hydrocarbon uwspomdon fuel. During the past quarter we have continued to design, prepare, characterize and test novel catalysts for the mild selective reaction of light hydrocarbons with air or oxygen to produce alcohols directly. These catalysts are designed to form active metal oxo (MO) species and to be uniquely active for the homolytic cleavage of the carbon-hydrogen bonds in light alkanes producing intermediates which can form alcohols. We continue to investigate three molecular environments for the active catalytic species that we are trying to generate: electron-deficient macrocycles (PHASE I), polyoxometallates (PHASE II), and regular oxidic lattices including zeolites and related structures as well as other molecular surface structures having metal oxo groups (PHASE I).

  1. Catalytic reforming feed characterisation technique

    Energy Technology Data Exchange (ETDEWEB)

    Larraz Mora, R.; Arvelo Alvarez, R. [Univ. of La Laguna, Chemical Engineering Dept., La Laguna (Spain)


    The catalytic reforming of naphtha is one of the major refinery processes, designed to increase the octane number of naphtha or to produce aromatics. The naphtha used as catalytic reformer feedstock usually contains a mixture of paraffins, naphthenes, and aromatics in the carbon number range C{sub 6} to C{sub 10}. The detailed chemical composition of the feed is necessary to predict the aromatics and hydrogen production as well as the operation severity. The analysis of feed naphtha is usually reported in terms of its ASTM distillation curve and API or specific gravity. Since reforming reactions are described in terms of lumped chemical species (paraffins, naphthenes and aromatics), a feed characterisation technique should be useful in order to predict reforming operating conditions and detect feed quality changes. Unfortunately online analyzer applications as cromatography or recently introduced naphtha NMR [1] are scarce in most of refineries. This work proposes an algorithmic characterisation method focusing on its main steps description. The method could help on the subjects previously described, finally a calculation example is shown. (orig.)

  2. [Acid-base catalysis of chiral Pd complexes: development of novel asymmetric reactions]. (United States)

    Hamashima, Yoshitaka


    Using a unique character of the chiral palladium complexes 1 and 2, several types of novel catalytic asymmetric reactions have been developed. In contrast to the conventional Pd(0)-catalyzed reactions, these complexes function as an acid-base catalyst. Thus active methine compounds were activated to form chiral palladium enolates, which underwent the enantioselective Michael reaction and Mannich-type reaction with up to 99% ee. Interestingly, these palladium enolates acted cooperatively with a strong protic acid activating the electrophiles, formed concomitantly during the formation of the enolates, whereby the C-C bond-forming reaction was promoted. In addition, this palladium enolate chemistry was also applicable to the electrophilic asymmetric fluorination reactions, and thus various carbonyl compounds including beta-ketoesters, beta-ketophosphonates, and oxindoles were fluorinated in a highly enantioselective manner (up to 98% ee). It is advantageous that these reactions were carried out in environmentally friendly alcoholic solvents such as ethanol, and exclusion of air and moisture is not necessary.

  3. Preview-based Asymmetric Load Reduction of Wind Turbines

    DEFF Research Database (Denmark)

    Madsen, Mathias; Filsø, Jakob; Soltani, Mohsen


    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...... to the same controller without LIDAR data. The results showed that the MPC with LIDAR was able to reduce the asymmetric loads compared to the MPC without LIDAR while still maintaining the power reference....

  4. Asymmetric joint multifractal analysis in Chinese stock markets (United States)

    Chen, Yuwen; Zheng, Tingting


    In this paper, the asymmetric joint multifractal analysis method based on statistical physics is proposed to explore the asymmetric correlation between daily returns and trading volumes in Chinese stock markets. The result shows asymmetric multifractal correlations exist between return and trading volume in Chinese stock markets. Moreover, when the stock indexes are upward, the fluctuations of returns are always weaker than when they are downward, whether the trading volumes are more or less.

  5. Combined shear/compression structural testing of asymmetric sandwich structures


    Castanié, Bruno; Barrau, Jean-Jacques; Jaouen, Jean-Pierre; Rivallant, Samuel


    Asymmetric sandwich technology can be applied in the design of lightweight, non-pressurized aeronautical structures such as those of helicopters. A test rig of asymmetric sandwich structures subjected to compression/shear loads was designed, validated, and set up. It conforms to the standard certification procedure for composite aeronautical structures set out in the “test pyramid”, a multiscale approach. The static tests until failure showed asymmetric sandwich structures to be extremely res...

  6. Asymmetric acoustic transmission in graded beam

    Energy Technology Data Exchange (ETDEWEB)

    Jing, Li, E-mail: [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Wu, Jiu Hui, E-mail: [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Guan, Dong; Lu, Kuan [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China); Gao, Nansha [School of Marine Science and Technology, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Songhua, Cao [School of Mechanical Engineering and State Key laboratory for Strength and Vibration of Mechanical Structures, Xi’an Jiaotong University, Xi’an, Shaanxi 710049 (China)


    We demonstrate the dynamic effective material parameters and vibration performance of a graded beam. The structure of the beam was composed of several unit cells with different fill factors. The dispersion relations and energy band structures of each unit cell were calculated using the finite element method (FEM). The dynamic effective material parameters in each unit cell of the graded beam were determined by the dispersion relations and energy band structures. Longitudinal wave propagation was investigated using a numerical method and FEM. The results show that the graded beam allows asymmetric acoustic transmission over a wide range of frequencies.

  7. On asymmetric causal relationships in Petropolitics

    Directory of Open Access Journals (Sweden)

    Balan Feyza


    Full Text Available The aim of this paper is to examine whether the First Law of Petropolitics denominated by Friedman in 2006 is valid for OPEC countries. To do this, this paper analyses the relationship between political risk and oil supply by applying the asymmetric panel causality test suggested by Hatemi-J (2011 to these countries for the period 1984-2014. The results show that the First Law of Petropolitics is valid for Angola, Iraq, Kuwait, Libya, Nigeria, Qatar, Saudi Arabia, and the UAE, given that positive oil supply shocks significantly lead to negative political stability shocks, and negative oil supply shocks significantly lead to positive shocks in political stability.

  8. RHIC operation with asymmetric collisions in 2015

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Aschenauer, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Atoian, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Blaskiewicz, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Brown, K. A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Bruno, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Connolly, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ottavio, T. D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Drees, K. A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Fischer, W. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gardner, C. J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gu, X. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hayes, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Huang, H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Laster, J. S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Luo, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Makdisi, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marr, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marusic, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Meot, F. [Brookhaven National Lab. (BNL), Upton, NY (United States); Mernick, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Michnoff, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Minty, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Montag, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Morris, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Narayan, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Nayak, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Nemesure, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Pile, P. [Brookhaven National Lab. (BNL), Upton, NY (United States); Poblaguev, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Ranjbar, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Robert-Demolaize, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Roser, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Schmidke, B. [Brookhaven National Lab. (BNL), Upton, NY (United States); Schoefer, V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Severino, F. [Brookhaven National Lab. (BNL), Upton, NY (United States); Shrey, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Smith, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Steski, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tepikian, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Trbojevic, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Tsoupas, N. [Brookhaven National Lab. (BNL), Upton, NY (United States); Wang, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); White, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Yip, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zaltsman, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zeno, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Zhang, S. Y. [Brookhaven National Lab. (BNL), Upton, NY (United States)


    To study low-x shadowing/saturation physics as well as other nuclear effects [1], [2], proton-gold (p-Au, for 5 weeks) and proton-Aluminum (p-Al, for 2 weeks) collisions were provided for experiments in 2015 at the Relativistic Heavy Ion Collider (RHIC), with polarized proton beam in the Blue ring and Au/Al beam in the Yellow ring. The special features of the asymmetric run in 2015 will be introduced. The operation experience will be reviewed as well in the report.

  9. Nanotribology of Symmetric and Asymmetric Liquid Lubricants

    Directory of Open Access Journals (Sweden)

    Shinji Yamada


    Full Text Available When liquid molecules are confined in a narrow gap between smooth surfaces, their dynamic properties are completely different from those of the bulk. The molecular motions are highly restricted and the system exhibits solid-like responses when sheared slowly. This solidification behavior is very dependent on the molecular geometry (shape of liquids because the solidification is induced by the packing of molecules into ordered structures in confinement. This paper reviews the measurements of confined structures and friction of symmetric and asymmetric liquid lubricants using the surface forces apparatus. The results show subtle and complex friction mechanisms at the molecular scale.

  10. Copper-catalyzed asymmetric oxidation of sulfides. (United States)

    O'Mahony, Graham E; Ford, Alan; Maguire, Anita R


    Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence of variation of solvent and ligand structure was examined, and the optimized conditions were then used to oxidize a number of aryl alkyl and aryl benzyl sulfides, producing sulfoxides in excellent yields in most cases (up to 92%), and good enantiopurities in certain cases (up to 84% ee).

  11. Catalytic gasification of dry and wet biomass

    NARCIS (Netherlands)

    van Rossum, G.; Potic, B.; Kersten, Sascha R.A.; van Swaaij, Willibrordus Petrus Maria


    Catalytic gasification of dry biomass and of wet biomass streams in hot compressed water are reviewed and discussed as potential technologies for the production of synthesis gas, hydrogen- and methane-rich gas. Next to literature data also new experimental results from our laboratory on catalytic

  12. Understanding catalytic biomass conversion through data mining

    NARCIS (Netherlands)

    Ras, E.J.; McKay, B.; Rothenberg, G.


    Catalytic conversion of biomass is a key challenge that we chemists face in the twenty-first century. Worldwide, research is conducted into obtaining bulk chemicals, polymers and fuels. Our project centres on glucose valorisation via furfural derivatives using catalytic hydrogenation. We present

  13. Heterogeneous catalytic degradation of polyacrylamide solution | Hu ...

    African Journals Online (AJOL)

    Modified with trace metal elements, the catalytic activity of Fe2O3/Al2O3 could be changed greatly. Among various trace metal elements, Fe2O3/Al2O3 catalysts modified with Co and Cu showed great increase on catalytic activity. International Journal of Engineering, Science and Technology, Vol. 2, No. 7, 2010, pp. 110- ...

  14. Electrochemical promotion of catalytic reactions (United States)

    Imbihl, R.


    The electrochemical promotion of heterogeneously catalyzed reactions (EPOC) became feasible through the use of porous metal electrodes interfaced to a solid electrolyte. With the O 2- conducting yttrium stabilized zirconia (YSZ), the Na + conducting β″-Al 2O 3 (β-alumina), and several other types of solid electrolytes the EPOC effect has been demonstrated for about 100 reaction systems in studies conducted mainly in the mbar range. Surface science investigations showed that the physical basis for the EPOC effect lies in the electrochemically induced spillover of oxygen and alkali metal, respectively, onto the surface of the metal electrodes. For the catalytic promotion effect general concepts and mechanistic schemes were proposed but these concepts and schemes are largely speculative. Applying surface analytical tools to EPOC systems the proposed mechanistic schemes can be verified or invalidated. This report summarizes the progress which has been achieved in the mechanistic understanding of the EPOC effect.

  15. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)


    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)


    Busey, H.M.


    A convection type recombiner is described for catalytically recombining hydrogen and oxygen which have been radiolytically decomposed in an aqueous homogeneous nuclear reactor. The device is so designed that the energy of recombination is used to circulate the gas mixture over the catalyst. The device consists of a vertical cylinder having baffles at its lower enda above these coarse screens having platinum and alumina pellets cemented thereon, and an annular passage for the return of recombined, condensed water to the reactor moderator system. This devicea having no moving parts, provides a simple and efficient means of removing the danger of accumulated hot radioactive, explosive gases, and restoring them to the moderator system for reuse.

  17. Fluctuations in catalytic surface reactions

    CERN Document Server

    Imbihl, R


    The internal reaction-induced fluctuations which occur in catalytic CO oxidation on a Pt field emitter tip have been studied using field electron microscopy (FEM) as a spatially resolving method. The structurally heterogeneous Pt tip consists of facets of different orientations with nanoscale dimensions. The FEM resolution of roughly 2 nm corresponds to a few hundred reacting adsorbed particles whose variations in the density are imaged as brightness fluctuations. In the bistable range of the reaction one finds fluctuation-induced transitions between the two stable branches of the reaction kinetics. The fluctuations exhibit a behaviour similar to that of an equilibrium phase transition, i.e. the amplitude diverges upon approaching the bifurcation point terminating the bistable range of the reaction. Simulations with a hybrid Monte Carlo/mean-field model reproduce the experimental observations. Fluctuations on different facets are typically uncorrelated but within a single facet a high degree of spatial cohere...

  18. Method of fabricating a catalytic structure (United States)

    Rollins, Harry W [Idaho Falls, ID; Petkovic, Lucia M [Idaho Falls, ID; Ginosar, Daniel M [Idaho Falls, ID


    A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.

  19. Ruthenium complexes with chiral tetradentate PNNP ligands: asymmetric catalysis from the viewpoint of inorganic chemistry. (United States)

    Mezzetti, Antonio


    This is a personal account of the application of ruthenium complexes containing chiral tetradentate ligands with a P(2)N(2) ligand set (PNNP) as catalyst precursors for enantioselective "atom transfer" reactions. Therewith are meant reactions that involve bond formation between a metal-coordinated molecule and a free reagent. The reactive fragment (e.g. carbene) is transferred either from the metal to the non-coordinated substrate (e.g. olefin) or from the free reagent (e.g. F(+)) to the metal-bound substrate (e.g.beta-ketoester), depending on the class of catalyst (monocationic, Class A; or dicationic, Class B). The monocationic five-coordinate species [RuCl(PNNP)](+) and the six-coordinate complexes [RuCl(L)(PNNP)](+) (L = Et(2)O, H(2)O) of Class A catalyse asymmetric epoxidation, cyclopropanation (carbene transfer from the metal to the free olefin), and imine aziridination. Alternatively, the dicationic complexes [Ru(L-L)(PNNP)](2+) (Class B), which contain substrates that act as neutral bidentate ligands L-L (e.g., beta-ketoesters), catalyse Michael addition, electrophilic fluorination, and hydroxylation reactions. Additionally, unsaturated beta-ketoesters form dicationic complexes of Class B that catalyse Diels-Alder reactions with acyclic dienes to produce tetrahydro-1-indanones and estrone derivatives. Excellent enantioselectivity has been achieved in several of the catalytic reactions mentioned above. The study of key reaction intermediates (both in the solid state and in solution) has revealed significant mechanistic aspects of the catalytic reactions.

  20. At Low SNR Asymmetric Quantizers Are Better

    CERN Document Server

    Koch, Tobias


    We study the capacity of the discrete-time Gaussian channel when its output is quantized with a one-bit quantizer. We focus on the low signal-to-noise ratio (SNR) regime, where communication at very low spectral efficiencies takes place. In this regime a symmetric threshold quantizer is known to reduce channel capacity by 2/pi, i.e., to cause an asymptotic power loss of approximately two decibels. Here it is shown that this power loss can be entirely avoided by using asymmetric threshold quantizers and asymmetric signaling constellations. We prove that in order to avoid this power loss flash-signaling input-distributions are essential. Consequently, one-bit output quantization of the Gaussian channel reduces spectral efficiency. Threshold quantizers are not only asymptotically optimal: as we prove, at every fixed SNR, a threshold quantizer maximizes capacity among all one-bit output quantizers. The picture changes on the Rayleigh-fading channel. In the noncoherent case we show that a one-bit output quantizer ...

  1. Asymmetric DSL Technology of Signal Transmission

    Directory of Open Access Journals (Sweden)

    Dražen Kovačević


    Full Text Available Asymmetric flow of information is the key feature of theADSL (Asymmetric Digital Subscriber Loop technology, i.e.higher data transmission rate towards the user than from theuser towards the network. Characteristic is the short messagesending by the user with a certain request to the se!Ver. These!Ver responds to the request by a significantly longer messageof various electronic forms (data, digitized speech, pictures orvideo. Therefore, this technology is most often used by smalland medium users. ADSL is currently the only commerciallyavailable DSL technology which is still experiencing the breakthroughon the seiVice market. It enables faster access to theInternet, LAN (Local Area Network, videoconferencing, VoD(Video on Demand and interactive multimedia. In order tostandardize such se/Vices, the !TU (International TelecommunicationsUnion G. 992.1 (standardized DMT-discrete multi-tone line coding technology and ANSJ (American NationalStandards Institution Tl.413-95!98 are used for ADSL. DMT(Discrete Multi Tone, as the more popular one, uses the linecoding technique, which splits a certain frequency range intoseveral sub-channels. Most of these sub-channels are used forupstream and downstream transmission of speech and data,whereas some are used as pilot signals or kept in rese/Ve. Suchmodulation technique expands the frequency spectrum, allowingthe usage ofbroadband se/Vices per one pair of wires. In thisway the sharing of speech and data se/Vice transmission is realized.

  2. Asymmetric Uncertainty Expression for High Gradient Aerodynamics (United States)

    Pinier, Jeremy T


    When the physics of the flow around an aircraft changes very abruptly either in time or space (e.g., flow separation/reattachment, boundary layer transition, unsteadiness, shocks, etc), the measurements that are performed in a simulated environment like a wind tunnel test or a computational simulation will most likely incorrectly predict the exact location of where (or when) the change in physics happens. There are many reasons for this, includ- ing the error introduced by simulating a real system at a smaller scale and at non-ideal conditions, or the error due to turbulence models in a computational simulation. The un- certainty analysis principles that have been developed and are being implemented today do not fully account for uncertainty in the knowledge of the location of abrupt physics changes or sharp gradients, leading to a potentially underestimated uncertainty in those areas. To address this problem, a new asymmetric aerodynamic uncertainty expression containing an extra term to account for a phase-uncertainty, the magnitude of which is emphasized in the high-gradient aerodynamic regions is proposed in this paper. Additionally, based on previous work, a method for dispersing aerodynamic data within asymmetric uncer- tainty bounds in a more realistic way has been developed for use within Monte Carlo-type analyses.

  3. Algebraic Davis Decomposition and Asymmetric Doob Inequalities (United States)

    Hong, Guixiang; Junge, Marius; Parcet, Javier


    In this paper we investigate asymmetric forms of Doob maximal inequality. The asymmetry is imposed by noncommutativity. Let {({M}, τ)} be a noncommutative probability space equipped with a filtration of von Neumann subalgebras {({M}_n)_{n ≥ 1}}, whose union {bigcup_{n≥1}{M}_n} is weak-* dense in {{M}}. Let {{E}_n} denote the corresponding family of conditional expectations. As an illustration for an asymmetric result, we prove that for {1 Hardy spaces {{H}_p^r({M})} and {{H}_p^c({M})} respectively. In particular, this solves a problem posed by the Defant and Junge in 2004. In the case p = 1, our results establish a noncommutative form of the Davis celebrated theorem on the relation betwe en martingale maximal and square functions in L 1, whose noncommutative form has remained open for quite some time. Given {1 ≤ p ≤ 2}, we also provide new weak type maximal estimates, which imply in turn left/right almost uniform convergence of {{E}_n(x)} in row/column Hardy spaces. This improves the bilateral convergence known so far. Our approach is based on new forms of Davis martingale decomposition which are of independent interest, and an algebraic atomic description for the involved Hardy spaces. The latter results are new even for commutative von Neumann algebras.

  4. [Asymmetric hypertrophy of the masticatory muscles]. (United States)

    Arzul, L; Corre, P; Khonsari, R H; Mercier, J-M; Piot, B


    Hypertrophy of the masticatory muscles most commonly affects the masseter. Less common cases of isolated or associated temporalis hypertrophy are also reported. Parafunctional habits, and more precisely bruxism, can favor the onset of the hypertrophy. This condition is generally idiopathic and can require both medical and/or surgical management. A 29-year-old patient was referred to our department for an asymmetric swelling of the masticatory muscles. Physical examination revealed a bilateral hypertrophy of the masticatory muscles, predominantly affecting the right temporalis and the left masseter. Major bruxism was assessed by premature dental wearing. The additional examinations confirmed the isolated muscle hypertrophy. Benign asymmetric hypertrophy of the masticatory muscles promoted by bruxism was diagnosed. Treatment with injections of type A botulinum toxin was conducted in association with a splint and relaxation. Its effectiveness has been observed at six months. Few cases of unilateral or bilateral temporalis hypertrophy have been reported, added to the more common isolated masseter muscles hypertrophy. The diagnosis requires to rule out secondary hypertrophies and tumors using Magnetic Resonance Imaging. The condition is thought to be favoured by parafunctional habits such as bruxism. The conservative treatment consists in reducing the volume of the masticatory muscles using intramuscular injections of type A botulinum toxin. Other potential conservative treatments are wearing splints and muscle relaxant drugs. Surgical procedures aiming to reduce the muscle volume and/or the bone volume (mandibular gonioplasty) can be proposed. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  5. An asymmetric B factory based on PEP

    Energy Technology Data Exchange (ETDEWEB)


    In this report we describe a design for a high-luminosity Asymmetric B Factory to be built in the PEP tunnel on the SLAC site. This proposal, a collaborative effort SLAC, LBL, and LLNL, is the culmination of more than two years of effort aimed at the design and construction of an asymmetric e{sup +}e{sup {minus}} collider capable of achieving a luminosity of L = 3 {times} 10{sup 33} cm{sup {minus}2} s{sup {minus}1}. The configuration adopted utilizes two storage rings, and electron ring operating at 9 GeV and a positron ring at 3.1 GeV, each with a circumference of 2200 m. The high-energy ring is an upgrade of the PEP storage ring at SLAC; all PEP magnets and most power supplies will be reused. The upgrade consists primarily of replacing the PEP vacuum chamber and RF system with newly designed versions optimized for the high-current environment of the B Factory. The low-energy ring will be newly constructed and will be situated atop the high-energy ring in the PEP tunnel. Utilities already installed in the PEP tunnel are largely sufficient to operate the two B Factory storage rings.

  6. Asymmetric inheritance of cytoophidia in Schizosaccharomyces pombe

    Directory of Open Access Journals (Sweden)

    Jing Zhang


    Full Text Available A general view is that Schizosaccharomyces pombe undergoes symmetric cell division with two daughter cells inheriting equal shares of the content from the mother cell. Here we show that CTP synthase, a metabolic enzyme responsible for the de novo synthesis of the nucleotide CTP, can form filamentous cytoophidia in the cytoplasm and nucleus of S. pombe cells. Surprisingly, we observe that both cytoplasmic and nuclear cytoophidia are asymmetrically inherited during cell division. Our time-lapse studies suggest that cytoophidia are dynamic. Once the mother cell divides, the cytoplasmic and nuclear cytoophidia independently partition into one of the two daughter cells. Although the two daughter cells differ from one another morphologically, they possess similar chances of inheriting the cytoplasmic cytoophidium from the mother cell, suggesting that the partition of cytoophidium is a stochastic process. Our findings on asymmetric inheritance of cytoophidia in S. pombe offer an exciting opportunity to study the inheritance of metabolic enzymes in a well-studied model system.

  7. Asymmetric Cell Divisions in the Epidermis (United States)

    Poulson, Nicholas D.; Lechler, Terry


    Generation of three-dimensional tissue with distinct cell types is required for the development of all organs. On its own, mitotic spindle orientation allows tissues to change in length or shape. In combination with intrinsic or extrinsic cues this can also be coupled to the generation of diverse cell fates - a process known as asymmetric cell division (ACD). Understanding ACD’s has been greatly aided by studies in invertebrate model systems, where genetics and live imaging have provided the basis for much of what we know. ACD’s also drive the development and differentiation of the epidermis in mammals. While similar to the invertebrate models, the epidermis is distinct in balancing symmetric and asymmetric divisions to yield a tissue of the correct surface area and thickness. Here we review the roles of spindle orientation in driving both morphogenesis and cell fate decisions. We highlight the epidermis as a unique model system to study not only basic mechanisms of ACD, but also to study their regulation during development. PMID:22449491

  8. Asymmetric Syntheses of Pharmaceuticals Containing a Cyclopropane Moiety Using Catalytic Asymmetric Simmons–Smith Reactions of Allylalcohols: Syntheses of Optically Active Tranylcypromine and Milnacipran

    National Research Council Canada - National Science Library

    Ishizuka, Yuki; Fujimori, Hirohisa; Noguchi, Takuya; Kawasaki, Masashi; Kishida, Mari; Nagai, Takuya; Imai, Nobuyuki; Kirihara, Masayuki


    ...–Smith cyclopropanation catalyzed by a simple disulfonamide derived from an α-amino acid. The optically active milnacipran was also synthesized by porcine pancreas lipase-catalyzed selective monoacylation of the C4-hydroxy group...

  9. Auxin as an inducer of asymmetrical division generating the subsidiary cells in stomatal complexes of Zea mays. (United States)

    Livanos, Pantelis; Giannoutsou, Eleni; Apostolakos, Panagiotis; Galatis, Basil


    The data presented in this work revealed that in Zea mays the exogenously added auxins indole-3-acetic acid (IAA) and 1-napthaleneacetic acid (NAA), promoted the establishment of subsidiary cell mother cell (SMC) polarity and the subsequent subsidiary cell formation, while treatment with auxin transport inhibitors 2,3,5-triiodobenzoic acid (TIBA) and 1-napthoxyacetic acid (NOA) specifically blocked SMC polarization and asymmetrical division. Furthermore, in young guard cell mother cells (GMCs) the PIN1 auxin efflux carriers were mainly localized in the transverse GMC faces, while in the advanced GMCs they appeared both in the transverse and the lateral ones adjacent to SMCs. Considering that phosphatidyl-inositol-3-kinase (PI3K) is an active component of auxin signal transduction and that phospholipid signaling contributes in the establishment of polarity, treatments with the specific inhibitor of the PI3K LY294002 were carried out. The presence of LY294002 suppressed polarization of SMCs and prevented their asymmetrical division, whereas combined treatment with exogenously added NAA and LY294002 restricted the promotional auxin influence on subsidiary cell formation. These findings support the view that auxin is involved in Z. mays subsidiary cell formation, probably functioning as inducer of the asymmetrical SMC division. Collectively, the results obtained from treatments with auxin transport inhibitors and the appearance of PIN1 proteins in the lateral GMC faces indicate a local transfer of auxin from GMCs to SMCs. Moreover, auxin signal transduction seems to be mediated by the catalytic function of PI3K.

  10. Insights into the asymmetric heterogeneous catalysis in porous organic polymers: constructing a TADDOL-embedded chiral catalyst for studying the structure-activity relationship. (United States)

    An, Wan-Kai; Han, Man-Yi; Wang, Chang-An; Yu, Si-Min; Zhang, Yuan; Bai, Shi; Wang, Wei


    Construction of porous organic polymers (POPs) as asymmetric catalysts remains as an important but challenging task. Herein, we exploit the "bottom-up" strategy to facilely synthesize an α,α,α',α'-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based chiral porous polymer (TADDOL-CPP) for highly efficient asymmetric catalysis. Constructed through the covalent linkages among the three-dimensional rigid monomers, TADDOL-CPP possesses hierarchical porous structure, high Brunauer-Emmett-Teller (BET) surface area, together with abundant and uniformly-distributed chiral sites. In the presence of [Ti(OiPr)4], TADDOL-CPP acts as a highly efficient and recyclable catalyst in the asymmetric addition of diethylzinc (Et2Zn) to aromatic aldehydes. Based on the direct observation of the key intermediates, the reaction mechanism has been revealed by solid-state (13)C magic-angle spinning (MAS) NMR spectroscopy. In combination with the catalytic testing results, characterization on the working catalyst provides further information for understanding the structure-activity relationship. We suggest that the catalytic activity of TADDOL-CPP is largely affected by the structural rigidity, cooperative catalysis, local chiral environment, and hierarchical porous framework. We expect that the information obtained herein will benefit to the designed synthesis of robust POP catalysts toward practical applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Decrease in back strength in asymmetric trunk postures

    NARCIS (Netherlands)

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


    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

  12. Catalytic reaction in confined flow channel

    Energy Technology Data Exchange (ETDEWEB)

    Van Hassel, Bart A.


    A chemical reactor comprises a flow channel, a source, and a destination. The flow channel is configured to house at least one catalytic reaction converting at least a portion of a first nanofluid entering the channel into a second nanofluid exiting the channel. The flow channel includes at least one turbulating flow channel element disposed axially along at least a portion of the flow channel. A plurality of catalytic nanoparticles is dispersed in the first nanofluid and configured to catalytically react the at least one first chemical reactant into the at least one second chemical reaction product in the flow channel.

  13. Asymmetric pair distribution functions in catalysts

    DEFF Research Database (Denmark)

    Clausen, B. S.; Nørskov, Jens Kehlet


    of asymmetric pair distribution functions for nano-sized particles and how they influence the structural parameters obtained from the standard data analysis. An alternative method, which takes into account deviations from the Gaussian pair distribution function typically used in the analysis of EXAFS spectra......, will be described. The method is based on an analysis of the pair distribution functions derived from molecular dynamics simulations of small metal particles and its reliability is demonstrated by comparing structural parameters obtained from independent X-ray diffraction experiments.......The structural parameters, i.e., coordination numbers, bond distances and disorder obtained from the analysis of EXAFS spectra may sometimes be significantly influenced by errors introduced due to the inadequacy of the analysis method applied. Especially in the case of heterogeneous catalysts...

  14. Polyimides Derived from Novel Asymmetric Benzophenone Dianhydrides (United States)

    Chuang, Chun-Hua (Inventor)


    This invention relates to the composition and processes for preparing thermoset polyimides derived from an asymmetric dianhydride, namely 2,3,3',4'-benzophenone dianhydride (a-BTDA) with at least one diamine, and a monofunctional terminal endcaps. The monofunctional terminating groups include 4-phenylethynylphthalic anhydride ester-acid derivatives, phenylethyl trimellitic anhydride (PETA) and its ester derivatives as well as 3-phenylethynylaniline. The process of polyimide composite comprises impregnating monomer reactants of dianhydride or its ester-acid derivatives, diamine and with monofunctional reactive endcaps into glass, carbon, quartz or synthetic fibers and fabrics, and then stack up into laminates and subsequently heated to between C. either at atmosphere or under pressure to promote the curing and crosslinking of the reactive endcaps to form a network of thermoset polyimides.

  15. Optical Nonreciprocity in Asymmetric Optomechanical Couplers (United States)

    Wang, Zheqi; Shi, Lei; Liu, Yi; Xu, Xinbiao; Zhang, Xinliang


    We propose an all-optical integrated nonreciprocal device on the optomechanical platform with a large nonreciprocal bandwidth and low operating power. The device is based on an asymmetric silicon coupler consisting of two branches. One of them is a conventional strip waveguide fixed on the substrate, and the other is a freestanding nanostring suspended above a groove in the substrate. When light is launched into the coupler, the optical gradient force between the freestanding nanostring and the underlying substrate leads to the deflection of the nanostring, and finally results in destruction of the initial phase-matching condition between the two branches. The suspended branch would achieve distinct deflections when light is incident from different ports. The simulation results show a nonreciprocal bandwidth of 13.1 nm with operating power of 390 μW. With the advantages of simple structure, low power consumption and large operating bandwidth, our work provides a promising solution for on-chip passive nonreciprocal device.

  16. Asymmetric adsorption in an open electrolytic cell (United States)

    Bousiadi, S.; Lelidis, I.


    We investigate the effect of adsorption-desorption phenomenon of ions in an asymmetric electrolytic cell at open circuit conditions. Our approach is based on the Poisson-Nernst-Planck theory for electrolytes and the kinetic model of Langmuir for the description of adsorption-desorption phenomena on the electrodes. When the electrodes are immersed into the solution, selective ion adsorption takes place. It is shown, that the selective ion adsorption is responsible for generating an electrical potential difference between the electrodes of the cell. The analytical expressions for the potential difference and for the charge distribution are calculated. Finally, the time evolution of the system is investigated and the relaxation times of the problem are deduced numerically.

  17. Bilateral asymmetrical traumatic sternoclavicular joint dislocations. (United States)

    Albarrag, Mohammed K


    Unilateral and bilateral sternoclavicular joint (SCJ) dislocations are rare injuries. The difficulty in assessing this condition often leads to delay in diagnosis and treatment. We report a rare case of bilateral asymmetrical traumatic SCJ dislocations in a 45-year-old male. The right anterior SCJ dislocation was reduced in the emergency room (ER) and resulted in residual instability. The left posterior SCJ dislocation was asymptomatic and unnoticed for six months. It is important for ER physicians and orthopaedic surgeons to be able identify and treat this condition. All suspected SCJ dislocations should be evaluated by computed tomography (CT) scan for confirmation of the diagnosis and evaluation of both SCJs. Posterior SCJ dislocation is a potentially fatal injury and should not be overlooked due to the presence of other injuries. Surgical intervention is often necessary in acute and old cases.

  18. Bilateral Asymmetrical Traumatic Sternoclavicular Joint Dislocations (United States)

    Albarrag, Mohammed K.


    Unilateral and bilateral sternoclavicular joint (SCJ) dislocations are rare injuries. The difficulty in assessing this condition often leads to delay in diagnosis and treatment. We report a rare case of bilateral asymmetrical traumatic SCJ dislocations in a 45-year-old male. The right anterior SCJ dislocation was reduced in the emergency room (ER) and resulted in residual instability. The left posterior SCJ dislocation was asymptomatic and unnoticed for six months. It is important for ER physicians and orthopaedic surgeons to be able identify and treat this condition. All suspected SCJ dislocations should be evaluated by computed tomography (CT) scan for confirmation of the diagnosis and evaluation of both SCJs. Posterior SCJ dislocation is a potentially fatal injury and should not be overlooked due to the presence of other injuries. Surgical intervention is often necessary in acute and old cases. PMID:23275851

  19. Asymmetrical Integration: Lessons from a Railway Empire. (United States)

    McDonald, Kate


    This article reexamines railway imperialism in Manchuria from the perspective of global network building. Through a case study of the Japanese-owned South Manchuria Railway Company (SMR), I trace how one railway empire used through traffic agreements to integrate Northeast Asian railways into a global network while at the same time installing itself as the necessary intermediary between European and Asian overland traffic. I argue that the SMR's pursuit of global reach and local dominance compels us to reconsider the traditional division of border-crossing railways into international and imperialist types, and instead to examine how border-crossing railways contributed to the uneven or "asymmetrical" integration of the global transportation infrastructure.

  20. Catalytic properties of Caucasian zeolites

    Energy Technology Data Exchange (ETDEWEB)

    Kostandyan, M.N.; Babayan, S.G.; Musaev, M.R.; Mirzoeva, K.G.


    Great deposits of natural zeolites have been discovered in the Caucasus which can be used in various fields of the economy. One promising direction of using them may be the field of petrochemistry. The results of research on the conversion of 1-hexanol in natural zeolites in the Caucasus have been reported previously. This work was carried out in order to obtain comparative data on the catalytic activity of zeolites from the following deposits: Novyy Kokhb in Armenia, Ay-Dag in Azerbaijan, and Khekordzula in Georgia. This established that without any preliminary chemical treatment these zeolites are good catalysts for the dehydration of primary hexyl alcohol and the isomerization of the l-hexene obtained into 2-hexene. The activity of all three catalysts is almost identical. Continuing the research in this direction, the conversion of cyclohexanol in the same natural zeolites has been studied. The conditions for carrying out the experiments and methodology of obtaining the reaction products are presented. The data obtained show that the degree of dehydration of cyclohexanol at low temperatures (250-350/sup 0/C) is significantly greater than the degree of dehydration of 1-hexanol. The dehydration is accompanied by skeletal isomerization into 1- and 3-methylcyclopentenes (a total of 3%). At high temperatures (400-450/sup 0/), along with an increased degree of isomerization of cyclohexene into methocyclopentenes, the formation of methylcyclopentane is observed as a result of the redistribution of hydrogen and coke on the catalysts. 1 reference.

  1. Introduction of Residue Fluid Catalytic Cracking Process

    National Research Council Canada - National Science Library



    .... Fluid catalytic cracking (FCC) is one of the most important conversion processes in a petroleum refinery, it also occupies very significant position in the refinery due to its economic benefits...

  2. Catalytic models developed through social work

    DEFF Research Database (Denmark)

    Jensen, Mogens


    The article develops the concept of catalytic processes in relation to social work with adolescents in an attempt to both reach a more nuanced understanding of social work and at the same time to develop the concept of catalytic processes in psychology. The social work is pedagogical treatment...... of adolescents placed in out-of-home care and is characterised using three situated cases as empirical data. Afterwards the concept of catalytic processes is briefly presented and then applied in an analysis of pedagogical treatment in the three cases. The result is a different conceptualisation of the social...... work with new possibilities of development of the work, but also suggestions for development of the concept of catalytic processes....

  3. Catalytic converters as a source of platinum

    Directory of Open Access Journals (Sweden)

    A. Fornalczyk


    Full Text Available The increase of Platinum Group Metals demand in automotive industry is connected with growing amount of cars equipped with the catalytic converters. The paper presents the review of available technologies during recycling process. The possibility of removing platinum from the used catalytic converters applying pyrometallurgical and hyrdometallurgical methods were also investigated. Metals such as Cu, Pb, Ca, Mg, Cd were used in the pyrometallurgical research (catalytic converter was melted with Cu, Pb and Ca or Mg and Cd vapours were blown through the whole carrier. In hydrometallurgical research catalytic converters was dissolved in aqua regia. Analysis of Pt contents in the carrier before and after the process was performed by means of atomic absorption spectroscopy. Obtained result were discussed.

  4. Catalytic iron and acute kidney injury. (United States)

    Leaf, David E; Swinkels, Dorine W


    Acute kidney injury (AKI) is a common and often devastating condition among hospitalized patients and is associated with markedly increased hospital length of stay, mortality, and cost. The pathogenesis of AKI is complex, but animal models support an important role for catalytic iron in causing AKI. Catalytic iron, also known as labile iron, is a transitional pool of non-transferrin-bound iron that is readily available to participate in redox cycling. Initial findings related to catalytic iron and animal models of kidney injury have only recently been extended to human AKI. In this review, we discuss the role of catalytic iron in human AKI, focusing on recent translational studies in humans, assay considerations, and potential therapeutic targets for future interventional studies. Copyright © 2016 the American Physiological Society.

  5. Catalytic ammonia oxidation to nitrogen (i) oxide




    The process of synthesis of nitrous oxide by low-temperature catalytical oxidation of NH has been investigated for organic synthesis. The investigation has been carried out by the stage separation approach with NH oxidation occurring in several reaction zones, which characterized by different catalytic conditions. The selectivity for N2O was 92-92,5% at the ammonia conversion of 98-99.5% in the optimal temperature range


    Directory of Open Access Journals (Sweden)

    Vedi V.E.


    Full Text Available The design and purpose of the basic units of the mobile waste processing complex “MPK” are described. Experimental data of catalytic purification of exhaust gases are presented. Experimental data on catalytic clearing of final gases of a designed mobile incinerator plant are shown. It is defined, that concentrating of parasitic bridging in waste gases of the complex are considerably smaller, rather than allowed by normative documents.

  7. Catalytic hydrogenation of carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Wayland, B.B.


    This project is focused on developing strategies to accomplish the reduction and hydrogenation of carbon monoxide to produce organic oxygenates at mild conditions. Our approaches to this issue are based on the recognition that rhodium macrocycles have unusually favorable thermodynamic values for producing a series of intermediate implicated in the catalytic hydrogenation of CO. Observations of metalloformyl complexes produced by reactions of H{sub 2} and CO, and reductive coupling of CO to form metallo {alpha}-diketone species have suggested a multiplicity of routes to organic oxygenates that utilize these species as intermediates. Thermodynamic and kinetic-mechanistic studies are used in constructing energy profiles for a variety of potential pathways, and these schemes are used in guiding the design of new metallospecies to improve the thermodynamic and kinetic factors for individual steps in the overall process. Variation of the electronic and steric effects associated with the ligand arrays along with the influences of the reaction medium provide the chemical tools for tuning these factors. Emerging knowledge of the factors that contribute to M-H, M-C and M-O bond enthalpies is directing the search for ligand arrays that will expand the range of metal species that have favorable thermodynamic parameters to produce the primary intermediates for CO hydrogenation. Studies of rhodium complexes are being extended to non-macrocyclic ligand complexes that emulate the favorable thermodynamic features associated with rhodium macrocycles, but that also manifest improved reaction kinetics. Multifunctional catalyst systems designed to couple the ability of rhodium complexes to produce formyl and diketone intermediates with a second catalyst that hydrogenates these imtermediates are promising approaches to accomplish CO hydrogenation at mild conditions.

  8. Adsorbent catalytic nanoparticles and methods of using the same

    Energy Technology Data Exchange (ETDEWEB)

    Slowing, Igor Ivan; Kandel, Kapil


    The present invention provides an adsorbent catalytic nanoparticle including a mesoporous silica nanoparticle having at least one adsorbent functional group bound thereto. The adsorbent catalytic nanoparticle also includes at least one catalytic material. In various embodiments, the present invention provides methods of using and making the adsorbent catalytic nanoparticles. In some examples, the adsorbent catalytic nanoparticles can be used to selectively remove fatty acids from feedstocks for biodiesel, and to hydrotreat the separated fatty acids.

  9. Homogenous asymmetric hydrogenation: Recent trends and industrial applications. (United States)

    Palmer, Andreas M; Zanotti-Gerosa, Antonio


    Recent advances in the field of homogeneous asymmetric hydrogenation are presented in this review. An analysis of academic literature published in the past 2 years highlights significant advances in the asymmetric hydrogenation of functional groups that previously were considered difficult to hydrogenate, as well as the emergence of novel concepts in catalysis, such as the use of non-traditional metals, phosphine-free catalysts and chiral counterions. An analysis of industry publications from 2009 and 2010 highlights more established applications of asymmetric hydrogenation reactions; these are discussed with a particular focus on practical aspects, such as catalyst selection, experimental conditions and the removal of metal residues.

  10. Coping with Asymmetric Channel Losses in CSMA/CA

    DEFF Research Database (Denmark)

    Paramanathan, Achuthan; Roetter, Daniel Enrique Lucani; Fitzek, Frank


    /CA is very sensitive to asymmetric channel losses caused by channel conditions. Leveraging this analysis, we present an adaptive channel priority protocol that copes with asymmetric channel losses while being compatible with CSMA/CA. We implement this protocol and perform real-life measurements that (i......) confirm the sensitivity of the CSMA/CA scheme in real implementations, and (ii) shows that our adaptive protocol provides a simple, yet potent mechanism to cope with asymmetric channel losses and ultimately to enhance end-to-end throughput in high-load scenarios....

  11. Generic approach for synthesizing asymmetric nanoparticles and nanoassemblies (United States)

    Sun, Yugang; Hu, Yongxing


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

  12. Asymmetric Branching in Biological Resource Distribution Networks (United States)

    Brummer, Alexander Byers

    There is a remarkable relationship between an organism's metabolic rate (resting power consumption) and the organism's mass. It may be a universal law of nature that an organism's resting metabolic rate is proportional to its mass to the power of 3/4. This relationship, known as Kleiber's Law, appears to be valid for both plants and animals. This law is important because it implies that larger organisms are more efficient than smaller organisms, and knowledge regarding metabolic rates are essential to a multitude of other fields in ecology and biology. This includes modeling the interactions of many species across multiple trophic levels, distributions of species abundances across large spatial landscapes, and even medical diagnostics for respiratory and cardiovascular pathologies. Previous models of vascular networks that seek to identify the origin of metabolic scaling have all been based on the unrealistic assumption of perfectly symmetric branching. In this dissertation I will present a theory of asymmetric branching in self-similar vascular networks (published by Brummer et al. in [9]). The theory shows that there can exist a suite of vascular forms that result in the often observed 3/4 metabolic scaling exponent of Kleiber's Law. Furthermore, the theory makes predictions regarding major morphological features related to vascular branching patterns and their relationships to metabolic scaling. These predictions are suggestive of evolutionary convergence in vascular branching. To test these predictions, I will present an analysis of real mammalian and plant vascular data that shows: (i) broad patterns in vascular networks across entire animal kingdoms and (ii) within these patterns, plant and mammalian vascular networks can be uniquely distinguished from one another (publication in preparation by Brummer et al.). I will also present results from a computational study in support of point (i). Namely, that asymmetric branching may be the optimal strategy to

  13. Asymmetric fluorination of α-branched cyclohexanones enabled by a combination of chiral anion phase-transfer catalysis and enamine catalysis using protected amino acids. (United States)

    Yang, Xiaoyu; Phipps, Robert J; Toste, F Dean


    We report a study involving the successful merger of two separate chiral catalytic cycles: a chiral anion phase-transfer catalysis cycle to activate Selectfluor and an enamine activation cycle, using a protected amino acid as organocatalyst. We have demonstrated the viability of this approach with the direct asymmetric fluorination of α-substituted cyclohexanones to generate quaternary fluorine-containing stereocenters. With these two chiral catalytic cycles operating together in a matched sense, high enantioselectivites can be achieved, and we envisage that this dual catalysis method has the potential to be more broadly applicable, given the breadth of enamine catalysis. It also represents a rare example of chiral enamine catalysis operating successfully on α-branched ketones, substrates commonly inert to this activation mode.

  14. Computation in Dynamically Bounded Asymmetric Systems (United States)

    Rutishauser, Ueli; Slotine, Jean-Jacques; Douglas, Rodney


    Previous explanations of computations performed by recurrent networks have focused on symmetrically connected saturating neurons and their convergence toward attractors. Here we analyze the behavior of asymmetrical connected networks of linear threshold neurons, whose positive response is unbounded. We show that, for a wide range of parameters, this asymmetry brings interesting and computationally useful dynamical properties. When driven by input, the network explores potential solutions through highly unstable ‘expansion’ dynamics. This expansion is steered and constrained by negative divergence of the dynamics, which ensures that the dimensionality of the solution space continues to reduce until an acceptable solution manifold is reached. Then the system contracts stably on this manifold towards its final solution trajectory. The unstable positive feedback and cross inhibition that underlie expansion and divergence are common motifs in molecular and neuronal networks. Therefore we propose that very simple organizational constraints that combine these motifs can lead to spontaneous computation and so to the spontaneous modification of entropy that is characteristic of living systems. PMID:25617645

  15. Asymmetric sensory reweighting in human upright stance.

    Directory of Open Access Journals (Sweden)

    David Logan

    Full Text Available To investigate sensory reweighting as a fundamental property of sensor fusion during standing, we probed postural control with simultaneous rotations of the visual scene and surface of support. Nineteen subjects were presented with pseudo-random pitch rotations of visual scene and platform at the ankle to test for amplitude dependencies in the following conditions: low amplitude vision: high amplitude platform, low amplitude vision: low amplitude platform, and high amplitude vision: low amplitude platform. Gain and phase of frequency response functions (FRFs to each stimulus were computed for two body sway angles and a single weighted EMG signal recorded from seven muscles. When platform stimulus amplitude was increased while visual stimulus amplitude remained constant, gain to vision increased, providing strong evidence for inter-modal reweighting between vision and somatosensation during standing. Intra-modal reweighting of vision was also observed as gains to vision decreased as visual stimulus amplitude increased. Such intra-modal and inter-modal amplitude dependent changes in gain were also observed in muscular activity. Gains of leg segment angle and muscular activity relative to the platform, on the other hand, showed only intra-modal reweighting. That is, changing platform motion amplitude altered the responses to both visual and support surface motion whereas changing visual scene motion amplitude did not significantly affect responses to support surface motion, indicating that the sensory integration scheme between somatosensation (at the support surface and vision is asymmetric.

  16. Asymmetric translation between multiple representations in chemistry (United States)

    Lin, Yulan I.; Son, Ji Y.; Rudd, James A., II


    Experts are more proficient in manipulating and translating between multiple representations (MRs) of a given concept than novices. Studies have shown that instruction using MR can increase student understanding of MR, and one model for MR instruction in chemistry is the chemistry triplet proposed by Johnstone. Concreteness fading theory suggests that presenting concrete representations before abstract representations can increase the effectiveness of MR instruction; however, little work has been conducted on varying the order of different representations during instruction and the role of concreteness in assessment. In this study, we investigated the application of concreteness fading to MR instruction and assessment in teaching chemistry. In two experiments, undergraduate students in either introductory psychology courses or general chemistry courses were given MR instruction on phase changes using different orders of presentation and MR assessment questions based on the representations in the chemistry triplet. Our findings indicate that the order of presentation based on levels of concreteness in MR chemistry instruction is less important than implementation of comprehensive MR assessments. Even after MR instruction, students display an asymmetric understanding of the chemical phenomenon on the MR assessments. Greater emphasis on MR assessments may be an important component in MR instruction that effectively moves novices toward more expert MR understanding.

  17. Biomechanical reevaluation of orthodontic asymmetric headgear. (United States)

    Chi, Lu; Cheng, Mulin; Hershey, H Garland; Nguyen, Tung; Ko, Ching-Chang


    To investigate the distribution of distal and lateral forces produced by orthodontic asymmetric headgear (AHG) using mathematical models to assess periodontal ligament (PDL) influence and to attempt to resolve apparent inconsistencies in the literature. Mechanical models for AHG were constructed to calculate AHG force magnitudes and direction using the theory of elasticity. The PDL was simulated by elastic springs attached to the inner-bow terminals of the AHG. The total storage energy (E(t)) of the AHG and the supporting springs was integrated to evaluate the distal and lateral forces produced by minimizing E(t) (Castigliano's theorem). All analytical solutions were derived symbolically. The spring-supported headgear model (SSHG) predicted the magnitude and distribution of distal forces consistent with our data and the published data of others. The SSHG model revealed that the lateral forces delivered to the inner-bow terminals were not equal, and the spring constant (stiffness of the PDL) affected the magnitude and direction of the resultant lateral forces. Changing the stiffness of the PDL produced a greater biomechanical effect than did altering the face-bow design. The PDL spring model appeared to help resolve inconsistencies in the literature between laboratory in vitro experiments and clinical in vivo studies. Force magnitude and direction of AHG were predicted precisely using the present model and may be applied to improve the design of AHG to minimize unwanted lateral tooth movement.

  18. Neural Network Control of Asymmetrical Multilevel Converters

    Directory of Open Access Journals (Sweden)

    Patrice WIRA


    Full Text Available This paper proposes a neural implementation of a harmonic eliminationstrategy (HES to control a Uniform Step Asymmetrical Multilevel Inverter(USAMI. The mapping between the modulation rate and the requiredswitching angles is learned and approximated with a Multi-Layer Perceptron(MLP neural network. After learning, appropriate switching angles can bedetermined with the neural network leading to a low-computational-costneural controller which is well suited for real-time applications. Thistechnique can be applied to multilevel inverters with any number of levels. Asan example, a nine-level inverter and an eleven-level inverter are consideredand the optimum switching angles are calculated on-line. Comparisons to thewell-known sinusoidal pulse-width modulation (SPWM have been carriedout in order to evaluate the performance of the proposed approach. Simulationresults demonstrate the technical advantages of the proposed neuralimplementation over the conventional method (SPWM in eliminatingharmonics while controlling a nine-level and eleven-level USAMI. Thisneural approach is applied for the supply of an asynchronous machine andresults show that it ensures a highest quality torque by efficiently cancelingthe harmonics generated by the inverters.

  19. Asymmetric evaluation promotes cooperation in network population (United States)

    Shen, Chen; Li, Xiaoping; Shi, Lei; Deng, Zhenghong


    The evolution of cooperation remains a fundamental challenge in human society. Many previous studies investigated these questions via spatial reciprocity, where players obtain their payoffs by interacting with their direct neighbors. It has also been verified that environmental factors can influence the evolution of cooperation theoretically and empirically. In reality, however, individuals may have the limit knowledge about their indirect neighbors. Inspired by this fact, we consider an asymmetric fitness calculation mechanism, which only integrates the environment factors into the focal player, to explore the evolution of cooperation. Here, the environmental factor is defined as the average payoff of all individual neighbors, which is regulated by a tunable parameter u. Through numerical simulation, we find that, compared with the traditional version (u = 0), that the cooperation level can be greatly enhanced when u is positive. Interestingly, the larger the value of u, the higher the level of cooperation. Finally, to explore the generality of this finding, we have tested the results on different topologies.

  20. Asymmetrically coupled resonators for mass sensing (United States)

    Marquez, S.; Alvarez, M.; Plaza, J. A.; Villanueva, L. G.; Dominguez, C.; Lechuga, L. M.


    Mechanically coupled resonators have been applied in the last years to the development of nanomechanical mass-sensors based on the detection of the different vibration modes of the system by measuring on a single resonator. Their sensitivity and capability for detecting multiple analytes strongly depends on the design and coupling strength between the mechanically coupled resonators in an array format. We present a theoretical and experimental study of the behavior of an asymmetrically coupled array of four different resonators. These doubly clamped beam resonators are elastically coupled by an overhang region of varying length along the transversal axis of the array. The results show that parameters such as the gap between microbeams and the overhang length affect the coupling strength, tuning the system from highly disordered and highly localized (weak coupling) to highly delocalized (strong coupling). In the strong coupling and partially localized case, the distances between resonant peaks are larger, reaching higher eigenfrequency values. In this case, relative changes in a specific eigenstate, due to an added mass, can be markedly large due to the energy distribution over a single microbeam. A strong coupling also facilitates performing the detection on the relative frequency shift mode, which can usually be resolved with better precision than the amplitude changes.

  1. Performance of an AGATA asymmetric detector

    Energy Technology Data Exchange (ETDEWEB)

    Boston, A.J. [Department of Physics, University of Liverpool, Liverpool L69 7ZE (United Kingdom)], E-mail:; Dimmock, M.R.; Unsworth, C.; Boston, H.C.; Cooper, R.J.; Grint, A.N.; Harkness, L.J. [Department of Physics, University of Liverpool, Liverpool L69 7ZE (United Kingdom); Lazarus, I.H. [STFC Daresbury Laboratory, Daresbury, Warrington WA4 4AD (United Kingdom); Jones, M.; Nolan, P.J.; Oxley, D.C. [Department of Physics, University of Liverpool, Liverpool L69 7ZE (United Kingdom); Simpson, J. [STFC Daresbury Laboratory, Daresbury, Warrington WA4 4AD (United Kingdom); Slee, M. [Department of Physics, University of Liverpool, Liverpool L69 7ZE (United Kingdom)


    High-resolution gamma-ray detectors based on high-purity germanium crystals (HPGe) are one of the key workhorses of experimental nuclear science. The technical development of such detector technology has been dramatic in recent years. Large volume, high-granularity, electrically segmented HPGe detectors have been realised and a methodology to improve position sensitivity using pulse-shape analysis coupled with the novel technique of gamma-ray tracking has been developed. Collaborations have been established in Europe (Advanced GAmma Tracking Array (AGATA)) [J. Simpson, Acta Phys. Pol. B 36 (2005) 1383] and the USA (GRETA/GRETINA) [C.W. Beausang, Nucl. Instr. and Meth. B 204 (2003)] to build gamma-ray tracking spectrometers. This paper discusses the performance of the first AGATA asymmetric detector that has been tested at the University of Liverpool. The use of a fully digital data acquisition system has allowed detector charge pulse shapes from a selection of well-defined photon interaction positions to be analysed, yielding important information on the position sensitivity of the detector.

  2. Micromagnetic simulation of Fe asymmetric nanorings

    Energy Technology Data Exchange (ETDEWEB)

    Palma, J.L.; Morales-Concha, C.; Leighton, B. [Departamento de Fisica, Universidad de Santiago de Chile (USACH), Avda. Ecuador 3493, 917-0124 Santiago (Chile); Altbir, D. [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); Escrig, J., E-mail: [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)


    During the last decade several methods to control the vortex chirality in nanodots have been proposed. One of them, the introduction of asymmetry in the geometry of the dots, originates interesting effects on the magnetic behavior of the particle. However, asymmetry in core-free structures is also interesting to investigate because of the reproducibility of their magnetic properties. In this work we report systematic changes in the coercivity and remanence in asymmetric nanorings. The angular dependence is also addressed. For specific geometries and magnetic field direction newly reversal modes appear associated with important changes in the coercivity and remanence of the rings. - Highlights: > We report that the existence of asymmetry strongly influences the coercivity and the remanence. > Magnetization reversal is driven by the nucleation of a C state and propagation of a vortex state. > We also conclude that the lack of a core contributes to the stability of the vortex state. > Asymmetry can be useful for tailoring specific magnetic characteristics of these systems.

  3. Trade Credit Insurance and Asymmetric Information Problem

    Directory of Open Access Journals (Sweden)

    Sokolovska Olena


    Full Text Available The presence of different risk factors in international trade gives evidence of the necessity of support in gaps that may affect exporters’ activity. To maximize the trade volumes and in the same time to minimize the exporters’ risks the stakeholders use trade credit insurance. The paper provides analysis of conceptual background of the trade credit insurance in the world. We analyzed briefly the problems, arising in insurance markets due to asymmetric information, such as adverse selection and moral hazard. Also we discuss the main stages of development of trade credit insurance in countries worldwide. Using comparative and graphical analysis we provide a brief evaluation of the dynamics of claims and recoveries for different forms of trade credit insurance. We found that the claims related to the commercial risk for medium and long trade credits in recent years exceed the recoveries, while with the political risk the reverse trend holds. And we originally consider these findings in terms of information asymmetry in the trade credit insurance differentiated by type of risk.

  4. High sensitivity field asymmetric ion mobility spectrometer. (United States)

    Chavarria, Mario A; Matheoud, Alessandro V; Marmillod, Philippe; Liu, Youjiang; Kong, Deyi; Brugger, Jürgen; Boero, Giovanni


    A high sensitivity field asymmetric ion mobility spectrometer (FAIMS) was designed, fabricated, and tested. The main components of the system are a 10.6 eV UV photoionization source, an ion filter driven by a high voltage/high frequency n-MOS inverter circuit, and a low noise ion detector. The ion filter electronics are capable to generate square waveforms with peak-to-peak voltages up to 1000 V at frequencies up to 1 MHz with adjustable duty cycles. The ion detector current amplifier has a gain up to 10 12 V/A with an effective equivalent input noise level down to about 1 fA/Hz 1/2 during operation with the ion filter at the maximum voltage and frequency. The FAIMS system was characterized by detecting different standard chemical compounds. Additionally, we investigated the use of a synchronous modulation/demodulation technique to improve the signal-to-noise ratio in FAIMS measurements. In particular, we implemented the modulation of the compensation voltage with the synchronous demodulation of the ion current. The analysis of the measurements at low concentration levels led to an extrapolated limit of detection for acetone of 10 ppt with an averaging time of 1 s.

  5. Evacuation dynamics of asymmetrically coupled pedestrian pairs

    CERN Document Server

    Müller, Frank


    We propose and analyze extended floor field cellular automaton models for evacuation dynamics of inhomogeneous pedestrian pairs which are coupled by asymmetric group interactions. Such pairs consist of a leader, who mainly determines the couple's motion and a follower, who has a defined tendency to follow the leader. Examples for such pairs are mother and child or two siblings of different age. We examine the system properties and compare them to the case of a homogeneous crowd. We find a strong impact on evacuation times for the regime of strong pair coupling due to the occurrence of a clogging phenomenon. In addition we obtain a non-trivial dependence of evacuation times on the followers' coupling to the static floor field, which carries the information of the shortest way to the exit location. In particular we find that systems with fully passive followers, who are solely coupled to their leaders, show lower evacuation times than homogeneous systems where all pedestrians have an equal tendency to move towa...

  6. High sensitivity field asymmetric ion mobility spectrometer (United States)

    Chavarria, Mario A.; Matheoud, Alessandro V.; Marmillod, Philippe; Liu, Youjiang; Kong, Deyi; Brugger, Jürgen; Boero, Giovanni


    A high sensitivity field asymmetric ion mobility spectrometer (FAIMS) was designed, fabricated, and tested. The main components of the system are a 10.6 eV UV photoionization source, an ion filter driven by a high voltage/high frequency n-MOS inverter circuit, and a low noise ion detector. The ion filter electronics are capable to generate square waveforms with peak-to-peak voltages up to 1000 V at frequencies up to 1 MHz with adjustable duty cycles. The ion detector current amplifier has a gain up to 1012 V/A with an effective equivalent input noise level down to about 1 fA/Hz1/2 during operation with the ion filter at the maximum voltage and frequency. The FAIMS system was characterized by detecting different standard chemical compounds. Additionally, we investigated the use of a synchronous modulation/demodulation technique to improve the signal-to-noise ratio in FAIMS measurements. In particular, we implemented the modulation of the compensation voltage with the synchronous demodulation of the ion current. The analysis of the measurements at low concentration levels led to an extrapolated limit of detection for acetone of 10 ppt with an averaging time of 1 s.

  7. Asymmetric Swiss-cheese brane-worlds (United States)

    Gergely, László Á.; Képíró, Ibolya


    We study a brane-world cosmological scenario with local inhomogeneities represented by black holes. The brane is asymmetrically embedded into the bulk. The black strings/cigars penetrating the Friedmann brane generate a Swiss-cheese-type structure. This universe forever expands and decelerates, as its general relativistic analogue. The evolution of the cosmological fluid, however, can proceed along four branches, two allowed to have positive energy density, and one of them having the symmetric embedding limit. On this branch a future pressure singularity can arise for either (a) a difference in the cosmological constants of the cosmological and black hole brane regions or (b) a difference in the left and right bulk cosmological constants. While behaviour (a) can be avoided by a redefinition of the fluid variables, (b) establishes a critical value of the asymmetry over which the pressure singularity occurs. We introduce the pressure singularity censorship which bounds the degree of asymmetry in the bulk cosmological constant. We also show as a model-independent generic feature that the asymmetry source term due to the bulk cosmological constant increases in the early universe. In order to obey the nucleosynthesis constraints, the brane tension should be constrained therefore both from below and from above. With the maximal degree of asymmetry obeying the pressure singularity censorship, the higher limit is ten times the lower limit. The degree of asymmetry allowed by present cosmological observations is, however, much less, pushing the upper limit to infinity.

  8. Experimental study of asymmetric heart valve prototype (United States)

    Vukicevic, M.; Fortini, S.; Querzoli, G.; Cenedese, A.; Pedrizzetti, G.


    The mechanical heart valves (MHVs) are extremely important medical devices, commonly used for diseased heart valves replacement. Despite the long term of use and constant design refinement, the MHVs are very far from ideal and their performance is very diverse from that of the native ones. It has been approved that small variations in geometry of valvular leaflets influence the significant change in the intraventricular vortical flow, known as one of the most important factors for the overall functionality of the heart. We have experimentally examined the home-made heart valve prototypes, exclusively modeled for the mitral valve replacement. The performance and energetic properties of the prototypes have been compared with those in the presence of standard MHVs. The analysis was based on the testing of intraventricular fluid dynamics, usually missing criteria for the quality of the valve performance. It has been shown that the asymmetric prototype, with unequal leaflets and D-shaped orifice produces flow patterns and energetic properties close to those found in the healthy subjects. Thus, the break of symmetry in the standard bi-leaflet MHV prosthesis, at least from the fluid dynamics point of view, is worthwhile to be considered for the design of MHVs for the mitral valve replacement.

  9. Cooperative Supply Chain Management Under Asymmetric Information

    Directory of Open Access Journals (Sweden)

    W.Y. Xu


    Full Text Available This study investigates supply chain cooperative management problem. In this study, based on principal-agent, firstly we analyses cooperative management factors in supply chain including leading enterprise expected utilities, subsidiary enterprise expected incomes and leading enterprise agency cost, then the incentive contract model is constructed; Secondly the model is solved in the case of symmetric information and asymmetric information; At last, in order to make clear of the model, this paper does mathematical analysis of leading enterprise expected utilities, subsidiary enterprise expected incomes and leading enterprise agency cost. Some important conclusions are obtained: subsidiary enterprise ability, cost coefficient, absolute risk aversion factor and output variance has the same influence on leading enterprise expected utilities and subsidiary enterprise expected incomes; subsidiary enterprise ability, cost coefficient has the same influence on leading enterprise expected utilities, subsidiary enterprise expected incomes and leading enterprise agency cost; leading enterprise expected utilities and subsidiary enterprise expected incomes become bigger and bigger, but leading enterprise agency cost becomes smaller and smaller with absolute risk aversion factor and output variance decreased. etc. Leading enterprise can take on incentive measures (improving subsidiary enterprise ability, decreasing subsidiary enterprise cost coefficient.etc to optimize supply chain management based on the common factors.

  10. Crystallization in mass and charge asymmetric bilayers (United States)

    Bonitz, Michael; Ludwig, Patrick; Filinov, Alexei; Lozovik, Yurii; Stolz, Heinrich


    We consider Coulomb crystal formation in quantum electron-ion (hole) bilayers. Varying the mass ratio M of ions and electrons between 1 and 100 for a fixed layer separation d at low temperature and high density, one can tune the hole behavior from delocalized (quantum) to localized (quasi-classical) while the electrons remain delocalized all the time. While in 3D plasmas [1], ions crystallize if the mass ratio exceeds a critical value of Mcr˜80, in bilayers Mcr can be drastically reduced by properly choosing d and the in-layer particle density. The complicated overlap of correlation and quantum effects of both, electrons and holes, is fully taken care of by performing first-principle path integral Monte Carlo simulations. [1] M. Bonitz, V.S. Filinov, V.E. Fortov. P.R. Levashov, and H. Fehske, Phys. Rev. Lett. 95, 235006 (2005) and J. Phys. A: Math. Gen. 39, 4717 (2006). [2] P. Ludwig, A. Filinov, Yu. Lozovik, H. Stolz, and M. Bonitz, Crystallization in mass-asymmetric electron-hole bilayers, Contrib. Plasma Phys. (2007), ArXiv: cond-mat/0611556

  11. Atomically Precise Metal Nanoclusters for Catalytic Application

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)


    The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily high selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au25(SR)18, Au28(SR)20, Au38(SR)24, Au99(SR)42, Au144(SR)60, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our

  12. SambVca 2. A Web Tool for Analyzing Catalytic Pockets with Topographic Steric Maps

    KAUST Repository

    Falivene, Laura


    Developing more efficient catalysts remains one of the primary targets of organometallic chemists. To accelerate reaching this goal, effective molecular descriptors and visualization tools can represent a remarkable aid. Here, we present a Web application for analyzing the catalytic pocket of metal complexes using topographic steric maps as a general and unbiased descriptor that is suitable for every class of catalysts. To show the broad applicability of our approach, we first compared the steric map of a series of transition metal complexes presenting popular mono-, di-, and tetracoordinated ligands and three classic zirconocenes. This comparative analysis highlighted similarities and differences between totally unrelated ligands. Then, we focused on a recently developed Fe(II) catalyst that is active in the asymmetric transfer hydrogenation of ketones and imines. Finally, we expand the scope of these tools to rationalize the inversion of enantioselectivity in enzymatic catalysis, achieved by point mutation of three amino acids of mononuclear p-hydroxymandelate synthase.

  13. Symmetry in Cascade Chirality-Transfer Processes: A Catalytic Atroposelective Direct Arylation Approach to BINOL Derivatives. (United States)

    Wang, Jin-Zheng; Zhou, Jin; Xu, Chang; Sun, Hongbin; Kürti, László; Xu, Qing-Long


    Herein we disclose a scalable organocatalytic direct arylation approach for the regio- and atroposelective synthesis of non-C2-symmetric 2,2'-dihydroxy-1,1'-binaphthalenes (BINOLs). In the presence of catalytic amounts of axially chiral phosphoric acids, phenols and naphthols are coupled with iminoquinones via a cascade process that involves sequential aminal formation, sigmatropic rearrangement, and rearomatization to afford enantiomerically enriched BINOL derivatives in good to excellent yields. Our studies suggest that the (local) symmetry of the initially formed aminal intermediate has a dramatic impact on the level of enantioinduction in the final product. Aminals with a plane of symmetry give rise to BINOL derivatives with significantly lower enantiomeric excess than unsymmetrical ones featuring a stereogenic center. Presumably asymmetric induction in the sigmatropic rearrangement step is significantly more challenging than during aminal formation. Sigmatropic rearrangement of the enantiomerically enriched aminal and subsequent rearomatization transfers the central chirality into axial chirality with high fidelity.

  14. Polarization dependent switching of asymmetric nanorings with a circular field

    Directory of Open Access Journals (Sweden)

    Nihar R. Pradhan


    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.

  15. Vertical Control and Parallel Trade under Asymmetric Information

    Directory of Open Access Journals (Sweden)

    Alessandro Avenali


    profits from the manufacturer to the wholesaler. Therefore, in R&D-intensive industries, such as pharmaceuticals, policy makers should anticipate the likely consequences of PT under asymmetric information on the long-run incentives to innovate.

  16. Asymmetric periflexural exanthema: A report in an adult patient

    Directory of Open Access Journals (Sweden)

    Zawar V


    Full Text Available Asymmetric periflexural exanthem (APE is a distinctive exanthem, probably viral in origin. It is largely a disease of childhood and is uncommon in adults. We report an adult man presenting with the typical clinical findings of APE.

  17. Loss Aversion and the Asymmetric Transmission of Monetary Policy

    DEFF Research Database (Denmark)

    Santoro, Emiliano; Petrella, Ivan; Pfajfar, Damjan


    There is widespread evidence that monetary policy exerts asymmetric effects on output over contractions and expansions in economic activity, while price responses display no sizeable asymmetry. To rationalize these facts we develop a dynamic general equilibrium model where households’ utility...

  18. Salt supply to and significance of asymmetric salt diapirs

    DEFF Research Database (Denmark)

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


    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...... 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...... sediments, the diapir extruded an overhang. Using the asymmetric Klodawa Salt Structure (KSS) in central Poland as a prototype, a series of analogue models were carried out to investigate the evolution history and salt supply driven by asymmetric differential loading. During extension of the model, a daipir...

  19. Luminosity lifetime at an asymmetric e +e - collider (United States)

    Porter, Frank C.


    The dependence of the luminosity on time is discussed for an asymmetric e +e - storage ring collider, with emphasis on single-particle scattering mechanisms for beam loss. The "optimal" filling strategy and average luminosity obtainable are also reviewed.

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

    KAUST Repository

    Zhao, Yujun


    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.

  1. Asymmetric wave transmission in a diatomic acoustic/elastic metamaterial

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bing; Tan, K. T., E-mail: [Department of Mechanical Engineering, The University of Akron, Akron, Ohio 44325-3903 (United States)


    Asymmetric acoustic/elastic wave transmission has recently been realized using nonlinearity, wave diffraction, or bias effects, but always at the cost of frequency distortion, direction shift, large volumes, or external energy. Based on the self-coupling of dual resonators, we propose a linear diatomic metamaterial, consisting of several small-sized unit cells, to realize large asymmetric wave transmission in low frequency domain (below 1 kHz). The asymmetric transmission mechanism is theoretically investigated, and numerically verified by both mass-spring and continuum models. This passive system does not require any frequency conversion or external energy, and the asymmetric transmission band can be theoretically predicted and mathematically controlled, which extends the design concept of unidirectional transmission devices.

  2. Asymmetric MRI Systems: Shim and RF Coil Designs

    National Research Council Canada - National Science Library

    Crozier, S


    We have recently introduced the concept of asymmetric clinical MRI systems. The potential advantages of these systems include a reduced perception of claustrophobia by patients and better physician access to the patient...

  3. Pseudo-Goldstone modes in isospin-asymmetric nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, T.D. [Univ. of Washington, Seattle, WA (United States); Broniowski, W. [H. Niewodniczanski Institute of Nuclear Physics, Cracow (Poland)


    The authors analyze the chiral limit in dense isospin-asymmetric nuclear matter. It is shown that the pseudo-Goldstone modes in this system are qualitatively different from the case of isospin-symmetric matter.

  4. Pseudo-Goldstone modes in isospin-asymmetric nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, T.D. [Washington Univ., Seattle, WA (United States). Dept. of Physics; Broniowski, W. [Institute of Nuclear Physics, Cracow (Poland)


    We analyze the chiral limit in dense isoptin-asymmetric nuclear matter. It is shown that the pseudo-Goldstone modes in this system are qualitatively different from the case of isospin-symmetric matter. (author). 20 refs.

  5. Influence of temperature gradients on charge transport in asymmetric nanochannels

    NARCIS (Netherlands)

    Benneker, Anne M.; Wendt, Hans David; Lammertink, Rob G.H.; Wood, Jeffery A.


    Charge selective asymmetric nanochannels are used for a variety of applications, such as nanofluidic sensing devices and energy conversion applications. In this paper, we numerically investigate the influence of an applied temperature difference over tapered nanochannels on the resulting charge

  6. Non-stationary probabilities for the asymmetric exclusion process on ...

    Indian Academy of Sciences (India)

    stationary probabilities for the asymmetric exclusion process on a ring. V B Priezzhev. Invited Talks:- Topic 4: Pattern formation in systems out of equilibrium (growth processes, fracture, hydrodynamic instabilities, chemical reactions, granular flows, etc ...

  7. Optical detection of asymmetric bacteria utilizing electro orientation


    Choi, Jae-Woo; Pu, Allen; Psaltis, Demetri


    We propose a bacterial detection scheme which uses no biochemical markers and can be applied in a Point-of-Care setting. The detection scheme aligns asymmetric bacteria with an electric field and detects the optical scattering.

  8. Loss aversion and the asymmetric transmission of monetary policy

    NARCIS (Netherlands)

    Gaffeo, E.; Petrella, I.; Pfajfar, D.; Santoro, E.

    There is widespread evidence that monetary policy exerts asymmetric effects on output over contractions and expansions in economic activity, while price responses display no sizeable asymmetry. To rationalize these facts we develop a dynamic general equilibrium model where households’ utility

  9. Asymmetric continuum extreme processes in solids and fluids

    CERN Document Server

    Teisseyre, Roman


    This book deals with a class of basic deformations in asymmetric continuum theory. It describes molecular deformations and transport velocities in fluids, strain deformations in solids as well as the molecular transport, important in fracture processes.

  10. Asymmetric radiation transfer based on linear light-matter interaction (United States)

    Jia, Zi-xun; Shuai, Yong; Zhang, Jia-hui; Tan, He-ping


    In this paper, asymmetric radiation transfer based on linear light-matter interaction has been proposed. Two naturally different numerical methods, finite difference time domain (FDTD) and rigorous coupled wave analysis (RCWA), are utilized to verify that asymmetric radiation transfer can exist for linear plasmonic meta-material. The overall asymmetry has been introduced to evaluate bifacial transmission. Physics for the asymmetric optical responses have been understood via electromagnetic field distributions. Dispersion relation for surface plasmon polariton (SPP) and temporal coupled mode theory (TCMT) have been employed to verify the physics discussed in the paper. Geometric effects and the disappearing of asymmetric transmission have also been investigated. The results gained herein broaden the cognition of linear optical system, facilitate the design of novel energy harvesting device.

  11. Asymmetric periflexural exanthema: A report in an adult patient


    Zawar V


    Asymmetric periflexural exanthem (APE) is a distinctive exanthem, probably viral in origin. It is largely a disease of childhood and is uncommon in adults. We report an adult man presenting with the typical clinical findings of APE.

  12. One-pot catalytic asymmetric borylation of unsaturated aldehyde-derived imines; functionalisation to homoallylic boronate carboxylate ester derivatives. (United States)

    Pujol, Alba; Calow, Adam D J; Batsanov, Andrei S; Whiting, Andrew


    The β-borylation reaction of α,β-unsaturated aldehyde-derived imines, formed in situ, has been studied using a one-pot methodology, as a route to β-boryl aldehydes. The instability of the β-boryl aldehydes meant that derivatisation was required and routes to both acetal derivatives and homoallylic boronates were examined. β-Boryl acetals were also found to be unstable, however, the formation of homoallylic boronate derivatives using an in situ imine hydrolysis-Wittig olefination protocol was found to be suitable, resulting in an efficient synthesis with high enantiomeric excesses.

  13. Hodge operator and asymmetric fluid in unbounded domains

    Directory of Open Access Journals (Sweden)

    I. Kondrashuk


    Full Text Available A system of equations modeling the stationary flow of an incompressible asymmetric fluid is studied for bounded domains of an arbitrary form. Based on the methods of Clifford analysis, we write the system of asymmetric fluid in the hypercomplex formulation and represent its solution in Clifford operator terms. We have significantly used Clifford algebra, and in particular the Hodge operator of the Clifford algebra to demonstrate the existence and uniqueness of the strong solution for arbitrary unbounded domains.

  14. Hodge operator and asymmetric fluid in unbounded domains

    Directory of Open Access Journals (Sweden)

    I. kondrashuk


    Full Text Available A system of equations modeling the stationary flow of an incompressible asymmetric fluid is studied for bounded domains of an arbitrary form. Based on the methods of Clifford analysis, we write the system of asymmetric fluid in the hypercomplex formulation and represent its solution in Clifford operator terms. We have significantly used Clifford algebra, and in particular the Hodge operator of the Clifford algebra to demonstrate the existence and uniqueness of the strong solution for arbitrary unbounded domains.

  15. Reduction of contact stresses using involute gears with asymmetric teeth

    Directory of Open Access Journals (Sweden)

    Jarmila VOJTKOVÁ


    Full Text Available Asymmetrical involute gears have a different value of the operating pressure angle for right and left side of the gear. These teeth are suitable for one direction of rotation. Such teeth enable to change the length of the generating line. They enable to improve the value of reduced radii of curvature. Asymmetrical teeth allow reducing the values of Hertz's pressures, especially on the root of the teeth. Hertz pressures are directly related to the asymmetry.

  16. Oil prices and economic activity: An asymmetric cointegration approach

    Energy Technology Data Exchange (ETDEWEB)

    Lardic, Sandrine [EconomiX-CNRS, University of Paris 10 (France); Mignon, Valerie [EconomiX-CNRS, University of Paris 10 (France); CEPII, Paris (France)


    The aim of this paper is to study the long-term relationship between oil prices and economic activity, proxied by GDP. To account for asymmetries existing in the links between the two variables, we propose an approach based on asymmetric cointegration. Our empirical analysis concerns the U.S. economy, but also the G7, Europe and Euro area economies. Results indicate that, while standard cointegration is rejected, there is evidence for asymmetric cointegration between oil prices and GDP. (author)

  17. Circular motion of asymmetric self-propelling particles. (United States)

    Kümmel, Felix; ten Hagen, Borge; Wittkowski, Raphael; Buttinoni, Ivo; Eichhorn, Ralf; Volpe, Giovanni; Löwen, Hartmut; Bechinger, Clemens


    Micron-sized self-propelled (active) particles can be considered as model systems for characterizing more complex biological organisms like swimming bacteria or motile cells. We produce asymmetric microswimmers by soft lithography and study their circular motion on a substrate and near channel boundaries. Our experimental observations are in full agreement with a theory of Brownian dynamics for asymmetric self-propelled particles, which couples their translational and orientational motion.

  18. Dynamic and Asymmetric Adjustment in Beef and Pork Prices


    Hahn, William F.


    Beef and pork prices at farm, wholesale and retail are examined for evidence of a dynamic and asymmetric price transmission using an endogenous switching model. Dynamic adjustment means that it take time for prices to adjust to changes in the market. Price transmission is asymmetric if the speed or completeness of price adjustment depends on the direction that the price or a related price is moving. Some of the previous research on price transmission in agricultural markets attempts to use ma...

  19. Asymmetric dominance and the stability of constructed preferences


    Anyuan Shen; Shuguang Liu


    In this research, we explore how experience with an "attraction set" of options, designed to elicit an asymmetric-dominance (attraction) effect, affects choice making in a second "compromise set" designed to elicit a compromise effect. In Experiment 1, when a compromise set was presented, subjects who had chosen an asymmetrically dominating option from an attraction set were less likely to surrender to the compromise heuristic than their counterparts who had chosen the equiv...

  20. Monoclonal antibodies specific for the different subunits of asymmetric acetylcholinesterase from chick muscle. (United States)

    Tsim, K W; Randall, W R; Barnard, E A


    The asymmetric (20S) acetylcholinesterase (AChE, EC from 1-day-old chick muscle, purified on a column on which was immobilised a monoclonal antibody (mAb) to chick brain AChE, was used to immunise mice. Eight mAbs against the muscle enzyme were hence isolated and characterised. Five antibodies (4A8, 1C1, 10B7, 7G8, and 8H11) recognise a 110-kilodalton (kDa) subunit with AChE catalytic activity, one antibody (7D11) recognises a 72-kDa subunit with pseudocholinesterase or butyrylcholinesterase (BuChE, EC catalytic activity, and two antibodies (6B6 and 7D7) react with the 58-kDa collagenous tail unit. Those three polypeptides can be recognised together in the 20S enzyme used, which is a hybrid AChE/BuChE oligomer. Antibodies 6B6 and 7D7 are specific for asymmetric AChE. Four of the mAbs recognising the 110-kDa subunit were reactive with it in immunoblots. Sucrose density gradient analysis of the antibody-enzyme complexes showed that the anti-110-kDa subunit mAbs cross-link multiple 20S AChE molecules to form large aggregates. In contrast, there is only a 2-3S increase in the sedimentation constant with the mAbs specific for the 72-kDa or for the 58-kDa subunit, suggesting that those subunits are more inaccessible in the structure to intermolecular cross-linking. The 4A8, 10B7, 7D11, and 7D7 mAbs showed cross-reactivity to the corresponding enzyme from quail muscle; however, none of the eight mAbs reacted with either enzyme type from mammalian muscle or from Torpedo electric organ. All eight antibodies showed immunocytochemical localisation of the AChE form at the neuromuscular junctions of chicken twitch muscles.

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

    Directory of Open Access Journals (Sweden)

    Diane P Genereux


    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.

  2. Formation of asymmetric vesicles via phospholipase D-mediated transphosphatidylation. (United States)

    Takaoka, Rina; Kurosaki, Haruko; Nakao, Hiroyuki; Ikeda, Keisuke; Nakano, Minoru


    Most biomembranes have an asymmetric structure with regard to phospholipid distribution between the inner and outer leaflets of the lipid bilayers. Control of the asymmetric distribution plays a pivotal role in several cellular functions such as intracellular membrane fusion and cell division. The mechanism by which membrane asymmetry and its alteration function in these transformation processes is not yet clear. To understand the significance of membrane asymmetry on trafficking and metabolism of intracellular vesicular components, a system that experimentally reproduces the asymmetric nature of biomembranes is essential. Here, we succeeded in obtaining asymmetric vesicles by means of transphosphatidylation reactions with phospholipase D (PLD), which acts exclusively on phosphatidylcholine (PC) present in the outer leaflet of vesicles. By treating PC vesicles with PLD in the presence of 1.7M serine and 0.3M ethanolamine, we obtained asymmetric vesicles that are topologically similar to intracellular vesicles containing phosphatidylserine and phosphatidylethanolamine in the cytosolic leaflet. PLD and other unwanted compounds could be removed by trypsin digestion followed by dialysis. Our established technique has a great advantage over conventional methods in that asymmetric vesicles can be provided at high yield and high efficiency, which is requisite for most physicochemical assays. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Electro Catalytic Oxidation (ECO) Operation

    Energy Technology Data Exchange (ETDEWEB)

    Morgan Jones


    The power industry in the United States is faced with meeting many new regulations to reduce a number of air pollutants including sulfur dioxide, nitrogen oxides, fine particulate matter, and mercury. With over 1,000 power plants in the US, this is a daunting task. In some cases, traditional pollution control technologies such as wet scrubbers and SCRs are not feasible. Powerspan's Electro-Catalytic Oxidation, or ECO{reg_sign} process combines four pollution control devices into a single integrated system that can be installed after a power plant's particulate control device. Besides achieving major reductions in emissions of sulfur dioxide (SO{sub 2}), nitrogen oxides (NOx), fine particulate matter (PM2.5) and mercury (Hg), ECO produces a highly marketable fertilizer, which can help offset the operating costs of the process system. Powerspan has been operating a 50-MW ECO commercial demonstration unit (CDU) at FirstEnergy Corp.'s R.E. Burger Plant near Shadyside, Ohio, since February 2004. In addition to the CDU, a test loop has been constructed beside the CDU to demonstrate higher NOx removal rates and test various scrubber packing types and wet ESP configurations. Furthermore, Powerspan has developed the ECO{reg_sign}{sub 2} technology, a regenerative process that uses a proprietary solvent to capture CO{sub 2} from flue gas. The CO{sub 2} capture takes place after the capture of NOx, SO{sub 2}, mercury, and fine particulate matter. Once the CO{sub 2} is captured, the proprietary solution is regenerated to release CO{sub 2} in a form that is ready for geological storage or beneficial use. Pilot scale testing of ECO{sub 2} began in early 2009 at FirstEnergy's Burger Plant. The ECO{sub 2} pilot unit is designed to process a 1-MW flue gas stream and produce 20 tons of CO{sub 2} per day, achieving a 90% CO{sub 2} capture rate. The ECO{sub 2} pilot program provided the opportunity to confirm process design and cost estimates, and prepare for large

  4. Highly Dense Isolated Metal Atom Catalytic Sites

    DEFF Research Database (Denmark)

    Chen, Yaxin; Kasama, Takeshi; Huang, Zhiwei


    Atomically dispersed noble-metal catalysts with highly dense active sites are promising materials with which to maximise metal efficiency and to enhance catalytic performance; however, their fabrication remains challenging because metal atoms are prone to sintering, especially at a high metal...... loading. A dynamic process of formation of isolated metal atom catalytic sites on the surface of the support, which was achieved starting from silver nanoparticles by using a thermal surface-mediated diffusion method, was observed directly by using in situ electron microscopy and in situ synchrotron X......-ray diffraction. A combination of electron microscopy images with X-ray absorption spectra demonstrated that the silver atoms were anchored on five-fold oxygen-terminated cavities on the surface of the support to form highly dense isolated metal active sites, leading to excellent reactivity in catalytic oxidation...

  5. Catalytic Organic Transformations Mediated by Actinide Complexes

    Directory of Open Access Journals (Sweden)

    Isabell S. R. Karmel


    Full Text Available This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

  6. Temperature Modulation of a Catalytic Gas Sensor

    Directory of Open Access Journals (Sweden)

    Eike Brauns


    Full Text Available The use of catalytic gas sensors usually offers low selectivity, only based on their different sensitivities for various gases due to their different heats of reaction. Furthermore, the identification of the gas present is not possible, which leads to possible misinterpretation of the sensor signals. The use of micro-machined catalytic gas sensors offers great advantages regarding the response time, which allows advanced analysis of the sensor response. By using temperature modulation, additional information about the gas characteristics can be measured and drift effects caused by material shifting or environmental temperature changes can be avoided. In this work a miniaturized catalytic gas sensor which offers a very short response time (<150 ms was developed. Operation with modulated temperature allows analysis of the signal spectrum with advanced information content, based on the Arrhenius approach. Therefore, a high-precise electronic device was developed, since theory shows that harmonics induced by the electronics must be avoided to generate a comprehensible signal.

  7. Porous media for catalytic renewable energy conversion (United States)

    Hotz, Nico


    A novel flow-based method is presented to place catalytic nanoparticles into a reactor by sol-gelation of a porous ceramic consisting of copper-based nanoparticles, silica sand, ceramic binder, and a gelation agent. This method allows for the placement of a liquid precursor containing the catalyst into the final reactor geometry without the need of impregnating or coating of a substrate with the catalytic material. The so generated foam-like porous ceramic shows properties highly appropriate for use as catalytic reactor material, e.g., reasonable pressure drop due to its porosity, high thermal and catalytic stability, and excellent catalytic behavior. The catalytic activity of micro-reactors containing this foam-like ceramic is tested in terms of their ability to convert alcoholic biofuel (e.g. methanol) to a hydrogen-rich gas mixture with low concentrations of carbon monoxide (up to 75% hydrogen content and less than 0.2% CO, for the case of methanol). This gas mixture is subsequently used in a low-temperature fuel cell, converting the hydrogen directly to electricity. A low concentration of CO is crucial to avoid poisoning of the fuel cell catalyst. Since conventional Polymer Electrolyte Membrane (PEM) fuel cells require CO concentrations far below 100 ppm and since most methods to reduce the mole fraction of CO (such as Preferential Oxidation or PROX) have CO conversions of up to 99%, the alcohol fuel reformer has to achieve initial CO mole fractions significantly below 1%. The catalyst and the porous ceramic reactor of the present study can successfully fulfill this requirement.

  8. Affective privilege: Asymmetric interference by emotional distracters

    Directory of Open Access Journals (Sweden)

    Crystal eReeck


    Full Text Available Numerous theories posit that affectively salient stimuli are privileged in their capacity to capture attention and disrupt ongoing cognition. Two underlying assumptions in this theoretical position are that the potency of affective stimuli transcends task boundaries (i.e., emotional distracters do not have to belong to a current task-set to disrupt processing and that there is an asymmetry between emotional and cognitive processing (i.e., emotional distracters disrupt cognitive processing, but not vice versa. These assumptions have remained largely untested, as common experimental probes of emotion-cognition interaction rarely manipulate task-relevance and only examine one side of the presumed asymmetry of interference. To test these propositions directly, a face-word Stroop protocol was adapted to independently manipulate (a the congruency between target and distracter stimulus features, (b the affective salience of distracter features, and (c the task-relevance of emotional compared to non-emotional target features. A three-way interaction revealed interdependent effects of distracter relevance, congruence, and affective salience. Compared to task-irrelevant distracters, task-relevant congruent distracters facilitated performance and task-relevant incongruent distracters impaired performance, but the latter effect depended on the nature of the target feature and task. Specifically, task-irrelevant emotional distracters resulted in equivalent performance costs as task-relevant non-emotional distracters, whereas task-irrelevant non-emotional distracters did not produce performance costs comparable to those generated by task-relevant emotional distracters. These results document asymmetric cross-task interference effects for affectively salient stimuli, supporting the notion of affective prioritization in human information processing.

  9. Asymmetric inhibitory treatment effects in multilingual aphasia. (United States)

    Goral, Mira; Naghibolhosseini, Maryam; Conner, Peggy S


    Findings from recent psycholinguistic studies of bilingual processing support the hypothesis that both languages of a bilingual are always active and that bilinguals continually engage in processes of language selection. This view aligns with the convergence hypothesis of bilingual language representation. Furthermore, it is hypothesized that when bilinguals perform a task in one language they need to inhibit their other, nontarget language(s) and that stronger inhibition is required when the task is performed in the weaker language than in the stronger one. The study of multilingual individuals who acquire aphasia resulting from a focal brain lesion offers a unique opportunity to test the convergence hypothesis and the inhibition asymmetry. We report on a trilingual person with chronic nonfluent aphasia who at the time of testing demonstrated greater impairment in her first acquired language (Persian) than in her third, later learned language (English). She received treatment in English followed by treatment in Persian. An examination of her connected language production revealed improvement in her grammatical skills in each language following intervention in that language, but decreased grammatical accuracy in English following treatment in Persian. The increased error rate was evident in structures that are used differently in the two languages (e.g., auxiliary verbs). The results support the prediction that greater inhibition is applied to the stronger language than to the weaker language, regardless of their age of acquisition. We interpret the findings as consistent with convergence theories that posit overlapping neuronal representation and simultaneous activation of multiple languages and with proficiency-dependent asymmetric inhibition in multilinguals.

  10. Asymmetric transfer of auditory perceptual learning

    Directory of Open Access Journals (Sweden)

    Sygal eAmitay


    Full Text Available Perceptual skills can improve dramatically even with minimal practice. A major and practical benefit of learning, however, is in transferring the improvement on the trained task to untrained tasks or stimuli, yet the mechanisms underlying this process are still poorly understood. Reduction of internal noise has been proposed as a mechanism of perceptual learning, and while we have evidence that frequency discrimination (FD learning is due to a reduction of internal noise, the source of that noise was not determined. In this study, we examined whether reducing the noise associated with neural phase locking to tones can explain the observed improvement in behavioural thresholds. We compared FD training between two tone durations (15 and 100 ms that straddled the temporal integration window of auditory nerve fibers upon which computational modeling of phase locking noise was based. Training on short tones resulted in improved FD on probe tests of both the long and short tones. Training on long tones resulted in improvement only on the long tones. Simulations of FD learning, based on the computational model and on signal detection theory, were compared with the behavioral FD data. We found that improved fidelity of phase locking accurately predicted transfer of learning from short to long tones, but also predicted transfer from long to short tones. The observed lack of transfer from long to short tones suggests the involvement of a second mechanism. Training may have increased the temporal integration window which could not transfer because integration time for the short tone is limited by its duration. Current learning models assume complex relationships between neural populations that represent the trained stimuli. In contrast, we propose that training-induced enhancement of the signal-to-noise ratio offers a parsimonious explanation of learning and transfer that easily accounts for asymmetric transfer of learning.

  11. cis-2,5-Diaminobicyclo[2.2.2]octane, a New Chiral Scaffold for Asymmetric Catalysis. (United States)

    Shaw, Subrata; White, James D


    Catalysis of widely used chemical transformations in which the goal is to obtain the product as a pure enantiomer has become a major preoccupation of synthetic organic chemistry over the past three decades. A large number of chiral entities has been deployed to this end, many with considerable success, but one of the simplest and most effective catalytic systems to have emerged from this effort is that based on a chiral diamine, specifically trans-1,2-diaminocyclohexane. While there have been attempts to improve upon this scaffold in asymmetric synthesis, few have gained the recognition needed to take their place alongside this classic diamine. The challenge is to design a scaffold that retains the assets of trans-1,2-diaminocyclohexane while enhancing its intrinsic chirality and maximizing the scope of its applications. It occurred to us that cis-2,5-diaminobicyclo[2.2.2]octane could be such a scaffold. Synthesis of this diamine in enantiopure form was completed from benzoic acid, and the (1R,2R,4R,5R) enantiomer was used in all subsequent experiments in this laboratory. Condensation of the diamine with various salicyl aldehydes generated imine derivatives which proved to be excellent "salen" ligands for encapsulation of transition and other metals. In total, 12 salen-metal complexes were prepared from this ligand, many of which were crystalline and three of which, along with the ligand itself, yielded to X-ray crystallography. An advantage of this ligand is that it can be tuned sterically or electronically to confer specific catalytic properties on the salen-metal complex, and this feature was used in several applications of our salen-metal complexes in asymmetric synthesis. Thus, replacement of one of the tert-butyl groups in each benzenoid ring of the salen ligand by a methoxy substituent enhanced the catalytic efficiency of a cobalt(II)-salen complex used in asymmetric cyclopropanation of 1,1-disubstituted alkenes; the catalyst was employed in an improved

  12. Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters

    KAUST Repository

    Hong, Allen Y.


    General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems.

  13. Catalytic burners in larger boiler appliances

    Energy Technology Data Exchange (ETDEWEB)

    Silversand, Fredrik; Persson, Mikael (Catator AB, Lund (Sweden))


    This project focuses on the scale up of a Catator's catalytic burner technology to enable retrofit installation in existing boilers and the design of new innovative combinations of catalytic burners and boilers. Different design approaches are discussed and evaluated in the report and suggestions are made concerning scale-up. Preliminary test data, extracted from a large boiler installation are discussed together with an accurate analysis of technical possibilities following an optimization of the boiler design to benefit from the advantages of catalytic combustion. The experimental work was conducted in close collaboration with ICI Caldaie (ICI), located in Verona, Italy. ICI is a leading European boiler manufacturer in the effect segment ranging from about 20 kWt to several MWt. The study shows that it is possibly to scale up the burner technology and to maintain low emissions. The boilers used in the study were designed around conventional combustion and were consequently not optimized for implementation of catalytic burners. From previous experiences it stands clear that the furnace volume can be dramatically decreased when applying catalytic combustion. In flame combustion, this volume is normally dimensioned to avoid flame impingement on cold surfaces and to facilitate completion of the gas-phase reactions. The emissions of nitrogen oxides can be reduced by decreasing the residence time in the furnace. Even with the over-dimensioned furnace used in this study, we easily reached emission values close to 35 mg/kWh. The emissions of carbon monoxide and unburned hydrocarbons were negligible (less than 5 ppmv). It is possible to decrease the emissions of nitrogen oxides further by designing the furnace/boiler around the catalytic burner, as suggested in the report. Simultaneously, the size of the boiler installation can be reduced greatly, which also will result in material savings, i.e. the production cost can be reduced. It is suggested to optimize the

  14. Catalytic gasification of oil-shales

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.; Avakyan, T. [I.M. Gubkin Russian State Univ. of Oil and Gas, Moscow (Russian Federation); Strizhakova, Yu. [Samara State Univ. (Russian Federation)


    Nowadays, the problem of complex usage of solid fossil fuels as raw materials for obtaining of motor fuels and chemical products is becoming increasingly important. A one of possible solutions of the problem is their gasification with further processing of gaseous and liquid products. In this work we have investigated the process of thermal and catalytic gasification of Baltic and Kashpir oil-shales. We have shown that, as compared with non-catalytic process, using of nickel catalyst in the reaction increases the yield of gas, as well as hydrogen content in it, and decreases the amount of liquid products. (orig.)

  15. Toward a catalytic site in DNA

    DEFF Research Database (Denmark)

    Jakobsen, Ulla; Rohr, Katja; Vogel, Stefan


    A number of functionalized polyaza crown ether building blocks have been incorporated into DNA-conjugates as catalytic Cu(2+) binding sites. The effect of the DNA-conjugate catalyst on the stereochemical outcome of a Cu(2+)-catalyzed Diels-Alder reaction will be presented.......A number of functionalized polyaza crown ether building blocks have been incorporated into DNA-conjugates as catalytic Cu(2+) binding sites. The effect of the DNA-conjugate catalyst on the stereochemical outcome of a Cu(2+)-catalyzed Diels-Alder reaction will be presented....

  16. Preliminary X-ray crystallographic studies of BthTX-II, a myotoxic Asp49-phospholipase A{sub 2} with low catalytic activity from Bothrops jararacussu venom

    Energy Technology Data Exchange (ETDEWEB)

    Corrêa, L. C.; Marchi-Salvador, D. P. [Departamento de Física e Biofísica, Instituto de Biociências, UNESP, CP 510, CEP 18618-000, Botucatu-SP (Brazil); Cintra, A. C. O.; Soares, A. M. [Departamento de Análises Clínicas, Toxicológicas e Bromatológicas, FCFRP, USP, Ribeirão Preto/SP (Brazil); Fontes, M. R. M., E-mail: [Departamento de Física e Biofísica, Instituto de Biociências, UNESP, CP 510, CEP 18618-000, Botucatu-SP (Brazil)


    A myotoxic Asp49-PLA{sub 2} with low catalytic activity from B. jararacussu (BthTX-II) was crystallized in the monoclinic crystal system; a complete X-ray diffraction data set was collected and a molecular-replacement solution was obtained. The oligomeric structure of BthTX-II resembles those of the Asp49-PLA{sub 2} PrTX-III and all bothropic Lys49-PLA{sub 2}s. For the first time, a complete X-ray diffraction data set has been collected from a myotoxic Asp49-phospholipase A{sub 2} (Asp49-PLA{sub 2}) with low catalytic activity (BthTX-II from Bothrops jararacussu venom) and a molecular-replacement solution has been obtained with a dimer in the asymmetric unit. The quaternary structure of BthTX-II resembles the myotoxin Asp49-PLA{sub 2} PrTX-III (piratoxin III from B. pirajai venom) and all non-catalytic and myotoxic dimeric Lys49-PLA{sub 2}s. In contrast, the oligomeric structure of BthTX-II is different from the highly catalytic and non-myotoxic BthA-I (acidic PLA{sub 2} from B. jararacussu). Thus, comparison between these structures should add insight into the catalytic and myotoxic activities of bothropic PLA{sub 2}s.

  17. Heterogeneous Catalytic Oligomerization of Ethylene (United States)

    Jan, Oliver Dennis

    increased with temperature, with 17 wt.% observed at 190ºC. Higher reaction temperatures led to the formation of odd-numbered oligomers primarily due to acid-catalyzed cracking reactions. In the range of space velocities tested, a moderate WHSV of 2.0 hr-1 resulted in a local maximum of 10.6 wt.% of liquid hydrocarbon yield. A moderate nickel loading of 3.4 wt.% also resulted in the highest liquid yield out of the three loadings tested (10.6 wt.%). The variation in nickel loading revealed the importance of having a synergistic balance of nickel and acid sites on the catalyst to maximize ethylene conversion and maintain high liquid hydrocarbon yield. Lastly, we used supercritical ethylene as both a solvent and as a reactant for ethylene oligomerization over two silica-alumina type catalysts: Ni-Hbeta and Ni-Al-SBA-15. Specifically, the effect of pressure and temperature on the overall conversion and product selectivity were evaluated in the range from 0 to 65 bar and 30 to 120ºC. At subcritical conditions, the ethylene conversion reached a plateau of around 50%. By increasing the pressure past the critical point of ethylene, the conversion drastically increased to 71%. The increased conversion can be attributed to the solubility of certain oligomers, namely butene, in supercritical ethylene that promotes desorption from catalytic active site before further oligomerization. We also tested a mesoporous catalyst, Ni-Al-SBA-15 and observed conversion trends analogous to that of Ni-Hbeta. At supercritical conditions, ethylene oligomerization over Ni-Al-SBA-15 was more selective towards the butene product, with nearly 74 wt.% butenes observed. The catalyst activity increased with temperature from 30ºC to 120ºC. The experiment conducted at 30ºC showed very little activity and ethylene conversion, however it effectively heavy molecular weight species from the catalyst. This condition, albeit being not effective for ethylene oligomerization, could be implemented as an in

  18. Novel Metal Nanomaterials and Their Catalytic Applications

    Directory of Open Access Journals (Sweden)

    Jiaqing Wang


    Full Text Available In the rapidly developing areas of nanotechnology, nano-scale materials as heterogeneous catalysts in the synthesis of organic molecules have gotten more and more attention. In this review, we will summarize the synthesis of several new types of noble metal nanostructures (FePt@Cu nanowires, Pt@Fe2O3 nanowires and bimetallic Pt@Ir nanocomplexes; Pt-Au heterostructures, Au-Pt bimetallic nanocomplexes and Pt/Pd bimetallic nanodendrites; Au nanowires, CuO@Ag nanowires and a series of Pd nanocatalysts and their new catalytic applications in our group, to establish heterogeneous catalytic system in “green” environments. Further study shows that these materials have a higher catalytic activity and selectivity than previously reported nanocrystal catalysts in organic reactions, or show a superior electro-catalytic activity for the oxidation of methanol. The whole process might have a great impact to resolve the energy crisis and the environmental crisis that were caused by traditional chemical engineering. Furthermore, we hope that this article will provide a reference point for the noble metal nanomaterials’ development that leads to new opportunities in nanocatalysis.

  19. Electrochemical Promotion of Catalytic Reactions Using

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bjerrum, Niels; Cleemann, Lars Nilausen


    This paper presents the results of a study on electrochemical promotion (EP) of catalytic reactions using Pt/C/polybenzimidazole(H3PO4)/Pt/C fuel cell performed by the Energy and Materials Science Group (Technical University of Denmark) during the last 6 years[1-4]. The development of our...... understanding of the nature of the electrochemical promotion is also presented....


    African Journals Online (AJOL)


    adsorption process on the catalytic site and the second, the breaking of the carbon-heteroatom bond leading to the heteroatom elimination. The adsorption process of thiiren have ... The calculation program is ICON 8 provided by the Quantum Chemistry. Program Exchange (QCPE 344) written by the Roald Hoffmann group.

  1. Dynamic Responsive Systems for Catalytic Function

    NARCIS (Netherlands)

    Vlatkovic, Matea; Collins, Beatrice S. L.; Feringa, Ben L.


    Responsive systems have recently gained much interest in the scientific community in attempts to mimic dynamic functions in biological systems. One of the fascinating potential applications of responsive systems lies in catalysis. Inspired by nature, novel responsive catalytic systems have been

  2. Catalytic dehydrogenations of ethylbenzene to styrene

    NARCIS (Netherlands)

    Kapteijn, F.; Makkee, M.; Nederlof, C.

    This research work on the catalytic dehydrogenation of ethylbenzene (EB) to styrene (ST) had a primary goal of developing improved catalysts for dehydrogenation processes both in CO2 as well as with O2 that can compete with the conventional dehydrogenation process in steam. In order to achieve this

  3. Catalytic kinetic spectrophotometric determination of trace copper ...

    African Journals Online (AJOL)

    A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically by measuring the decrease in the absorbance of CPApA at the wavelength of 554 nm using the fixed-time method. The optimum reaction conditions ...

  4. Synthesis, spectroscopic characterization and catalytic oxidation ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 3. Synthesis, spectroscopic characterization and catalytic oxidation properties of ONO/ONS donor Schiff base ruthenium(III) complexes containing PPh3/AsPh3. Priyarega M Muthu Tamizh R Karvembu R Prabhakaran K Natarajan. Volume 123 Issue 3 May ...

  5. Lignin Valorization using Heterogenous Catalytic Oxidation

    DEFF Research Database (Denmark)

    Melián Rodríguez, Mayra; Shunmugavel, Saravanamurugan; Kegnæs, Søren

    is complex so different model compounds are often used to study lignin valorization. These model compounds contain the linkages present in lignin, simplifying catalytic analysis and present analytical challenges related to the study of the complicated lignin polymer and the plethora of products that could...

  6. Reversible Electrochemical Modulation of a Catalytic Nanosystem. (United States)

    Della Sala, Flavio; Chen, Jack L-Y; Ranallo, Simona; Badocco, Denis; Pastore, Paolo; Ricci, Francesco; Prins, Leonard J


    A catalytic system based on monolayer-functionalized gold nanoparticles (Au NPs) that can be electrochemically modulated and reversibly activated is reported. The catalytic activity relies on the presence of metal ions (Cd(2+) and Cu(2+) ), which can be complexed by the nanoparticle-bound monolayer. This activates the system towards the catalytic cleavage of 2-hydroxypropyl-p-nitrophenyl phosphate (HPNPP), which can be monitored by UV/Vis spectroscopy. It is shown that Cu(2+) metal ions can be delivered to the system by applying an oxidative potential to an electrode on which Cu(0) was deposited. By exploiting the different affinity of Cd(2+) and Cu(2+) ions for the monolayer, it was also possible to upregulate the catalytic activity after releasing Cu(2+) from an electrode into a solution containing Cd(2+) . Finally, it is shown that the activity of this supramolecular nanosystem can be reversibly switched on or off by oxidizing/reducing Cu/Cu(2+) ions under controlled conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Synthesis, spectroscopic characterization and catalytic oxidation ...

    Indian Academy of Sciences (India)

    of porphyrin containing enzymes.6 Though metallo- porphyrins catalyse oxidation reactions, the catalytic yield is not satisfactory to have any commercial viabil- ity. Moreover, it is not easy to synthesize metallopor- phyrins and this led scientists to look for other ligands to make novel complexes to be employed as catalysts.

  8. Electrochemical promotion of sulfur dioxide catalytic oxidation

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm


    The effect of electrochemical polarization on the catalytic SO2 oxidation in the molten V2O5-K2S2O7 system has been studied using a gold working electrode in the temperature range 400-460 degrees C. A similar experiment has been performed with the industrial catalyst VK-58. The aim of the present...

  9. Fluid catalytic cracking : Feedstocks and reaction mechanism

    NARCIS (Netherlands)

    Dupain, X.


    The Fluid Catalytic Cracking (FCC) process is one of the key units in a modern refinery. Traditionally, its design is primarily aimed for the production of gasoline from heavy oil fractions, but as co-products also diesel blends and valuable gasses (e.g. propene and butenes) are formed in

  10. Enhancement of reaction rates for catalytic benzaldehyde ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 2. Enhancement of reaction rates for catalytic benzaldehyde hydrogenation and sorbitol dehydration in water solvent by addition of carbon dioxide. Masayuki Shirai Osamu Sato Norihito Hiyoshi Aritomo Yamaguchi. Volume 126 Issue 2 March 2014 pp 395- ...

  11. Toward Facilitative Mentoring and Catalytic Interventions (United States)

    Smith, Melissa K.; Lewis, Marilyn


    In TESOL teacher mentoring, giving advice can be conceptualized as a continuum, ranging from directive to facilitative feedback. The goal, over time, is to lead toward the facilitative end of the continuum and specifically to catalytic interventions that encourage self-reflection and autonomous learning. This study begins by examining research on…

  12. Rapid Deployment of Rich Catalytic Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Richard S. Tuthill


    The overall objective of this research under the Turbines Program is the deployment of fuel flexible rich catalytic combustion technology into high-pressure ratio industrial gas turbines. The resulting combustion systems will provide fuel flexibility for gas turbines to burn coal derived synthesis gas or natural gas and achieve NO{sub x} emissions of 2 ppmvd or less (at 15 percent O{sub 2}), cost effectively. This advance will signify a major step towards environmentally friendly electric power generation and coal-based energy independence for the United States. Under Phase 1 of the Program, Pratt & Whitney (P&W) performed a system integration study of rich catalytic combustion in a small high-pressure ratio industrial gas turbine with a silo combustion system that is easily scalable to a larger multi-chamber gas turbine system. An implementation plan for this technology also was studied. The principal achievement of the Phase 1 effort was the sizing of the catalytic module in a manner which allowed a single reactor (rather than multiple reactors) to be used by the combustion system, a conclusion regarding the amount of air that should be allocated to the reaction zone to achieve low emissions, definition of a combustion staging strategy to achieve low emissions, and mechanical integration of a Ceramic Matrix Composite (CMC) combustor liner with the catalytic module.

  13. Enhancement of reaction rates for catalytic benzaldehyde ...

    Indian Academy of Sciences (India)

    Enhancement of reaction rates for catalytic benzaldehyde hydrogenation and sorbitol dehydration in water solvent by addition of carbon dioxide. MASAYUKI SHIRAIa,b,∗, OSAMU SATOa, NORIHITO HIYOSHIa and. ARITOMO YAMAGUCHIa. aResearch Center for Compact Chemical System, National Institute of Advanced ...

  14. State of supported rhodium nanoparticles for methane catalytic partial oxidation (CPO): FT-IR studies. (United States)

    Finocchio, Elisabetta; Busca, Guido; Forzatti, Pio; Groppi, Gianpiero; Beretta, Alessandra


    The effect of pretreatments as well as of rhodium precursor and of the support over the morphology of Rh nanoparticles were investigated by Fourier transform infrared (FT-IR) spectroscopy of adsorbed CO. Over a Rh/alumina catalyst, both metallic Rh particles, characterized by IR bands in the range 2070-2060 cm-1 and 1820-1850 cm-1, and highly dispersed rhodium species, characterized by symmetric and asymmetric stretching bands of RhI(CO)2 gem-dicarbonyl species, are present. Their relative amount changes following pretreatments with gaseous mixtures, representative of the catalytic partial oxidation (CPO) reaction process. The Rh metal particle fraction decreases with respect to the Rh highly dispersed fraction in the order CO approximately CO/H2 > CH4/H2O, CH4/O2 > CH4 > H2. The metal particle dimensions decrease in the order CH4/O2 > H2 > CH4/H2O > CO > CO/H2. Grafting from a carbonyl rhodium complex also increases the amount and the dimensions of Rh0 particles at the catalyst surface. Increasing the ratio (extended rhodium metal particles/highly dispersed Rh species) allows a shorter conditioning process. The surface reconstruction phenomena going on during catalytic activity are related to this effect.

  15. Stereospecific synthesis and catalytic activity of L-histidylidene metal complexes. (United States)

    Monney, Angèle; Alberico, Elisabetta; Ortin, Yannick; Müller-Bunz, Helge; Gladiali, Serafino; Albrecht, Martin


    We report on the synthesis, metal coordination, and catalytic impact of histidylidene, a histidine-derived N-heterocyclic carbene (NHC) ligand. The histidinium salt 3, comprising methyl substituents at both heterocyclic nitrogens and protected at the C- and N-terminus of the amino acid, was rhodated and iridated by a transmetallation protocol using Ag(2)O. Ambient temperature and short reaction times were pivotal for full retention of configuration at the α-carbon. The stereospecificity of the reaction was conveniently probed by (31)P NMR spectroscopy after transmetallation with rhodium(I) and coordination of enantiopure (S)-Ph-binepine. The histidylidene rhodium complexes are highly efficient catalysts for the mild hydrosilylation of ketones. For the cationic complexes [Rh(cod)(histidylidene)(phosphine)](+), lowering the temperature shifted the rate-limiting step of the catalytic reaction to an earlier stage that is not enantioselective. Hence the asymmetric induction-which is governed by the chiral phosphine-did not improve at low temperature.

  16. The Nudix Hydrolase CDP-Chase, a CDP-Choline Pyrophosphatase, Is an Asymmetric Dimer with Two Distinct Enzymatic Activities

    Energy Technology Data Exchange (ETDEWEB)

    Duong-Ly, Krisna C.; Gabelli, Sandra B.; Xu, WenLian; Dunn, Christopher A.; Schoeffield, Andrew J.; Bessman, Maurice J.; Amzel, L. Mario (Loyola); (JHU)


    A Nudix enzyme from Bacillus cereus catalyzes the hydrolysis of CDP-choline to produce CMP and phosphocholine. Here, we show that in addition, the enzyme has a 3{prime} {yields} 5{prime} RNA exonuclease activity. The structure of the free enzyme, determined to a 1.8-{angstrom} resolution, shows that the enzyme is an asymmetric dimer. Each monomer consists of two domains, an N-terminal helical domain and a C-terminal Nudix domain. The N-terminal domain is placed relative to the C-terminal domain such as to result in an overall asymmetric arrangement with two distinct catalytic sites: one with an 'enclosed' Nudix pyrophosphatase site and the other with a more open, less-defined cavity. Residues that may be important for determining the asymmetry are conserved among a group of uncharacterized Nudix enzymes from Gram-positive bacteria. Our data support a model where CDP-choline hydrolysis is catalyzed by the enclosed Nudix site and RNA exonuclease activity is catalyzed by the open site. CDP-Chase is the first identified member of a novel Nudix family in which structural asymmetry has a profound effect on the recognition of substrates.

  17. Asymmetrical dimethylarginine level in atrial fibrillation. (United States)

    Cengel, Atiye; Sahinarslan, Asife; Biberoğlu, Gursel; Hasanoğlu, Alev; Tavil, Yusuf; Tulmaç, Murat; Ozdemir, Murat


    Atrial fibrillation (AF) is known to be related with increased risk of thromboembolic events. Asymmetrical dimethylarginine (ADMA), which is an endogenous inhibitor of nitric oxide synthase (NOS), can cause endothelial dysfunction by decreasing nitric oxide (NO) and lead to increased risk of thrombosis. In the present study our aim was to compare plasma levels of ADMA in patients with acute onset ( 1 year) to determine the risk of thrombosis. 17 patients with the first detected attack of AF within the first 24 hours of presentation (group 1), 25 patients who had permanent chronic AF lasting at least 1 year or more (group II) and 18 healthy persons as the control group (group III) were included in the study. For each patient the plasma ADMA, L-arginine, symmetrical dimethylarginine (SDMA) concentrations were measured by high-performance liquid chromatography in venous blood samples collected before cardioversion. We compared the plasma ADMA, L-arginine and SDMA concentrations between the groups. Plasma L-arginine (78.18 +/- 28.29 vs. 73.14 +/- 14.11 vs. 71.03 +/- 21.31, P = 0.549) and plasma SDMA concentrations (0.38 +/-0.18 vs. 0.42 +/- 0.21 vs. 0.32 +/- 0.24, P = 0.224) were similar in all groups. There was a significant difference between plasma ADMA concentrations (0.76 +/- 0.27 vs. 0.50 +/- 0.26 vs. 0.36 +/- 0.20, P < 0.001) among the groups. When we compared plasma ADMA levels between the subgroups, we also found a significant difference (P = 0.002 when comparing group I and group II, P < 0.001 when comparing of group I and group III, P = 0.042 when compareng of group II and group III). ADMA levels in patients with acute onset AF were significantly increased when compared with patients with chronic AF and the healthy control group indicating the presence of endothelial dysfunction and a prothrombotic state even in a very early phase of AF.

  18. Asymmetric dimethylarginine and coronary collateral vessel development. (United States)

    Kocaman, Sinan Altan; Sahinarslan, Asife; Biberoglu, Gursel; Hasanoglu, Alev; Akyel, Ahmet; Timurkaynak, Timur; Cengel, Atiye


    Nitric oxide (NO) plays a major role in collateral vessel development. Asymmetric dimethylarginine (ADMA) that is an endogenous inhibitor of NO synthesis may impair the effective coronary collateral vessel development. The aim of this study was to evaluate the relationship between plasma ADMA level and coronary collateral vessel development. The patients with a greater than or equal to 95% obstruction in at least one epicardial coronary artery were included in the study. Degree of coronary collateral development was determined according to Rentrop method. Patients with grade 2-3 collateral development were regarded as good collateral group and formed group I. The patients with grade 0-1 collateral development were regarded as poor collateral group and were included in group II. Group III that had been formed as a control group included the patients with a normal coronary angiogram. We compared the plasma ADMA, symmetric dimethylarginine, L-arginine/ADMA ratio among three groups. Seventy-four patients have been included in the study. Patients with good collateral development had lower plasma ADMA level in comparison with patients with poor collateral development (0.41+/-0.25 micromol/l vs. 0.70+/-0.23 micromol/l, P=0.001) and had similar plasma ADMA levels with the patients who have normal coronary arteries. When we compared L-arginine/ADMA ratio between good and poor collateral groups, we found that the patients with higher L-arginine/ADMA ratio have significantly better collateral development (270.8+/-168.0 vs. 120.9+/-92.1, P<0.001). In the analyses comparing Rentrop score with ADMA level and L-arginine/ADMA ratio, there were significant correlations (r=-0.444, P=0.008 and r=0.553, P=0.001, respectively). In multivariate analysis, ADMA level (odds ratio, 0.009; 95% confidence interval, 0.000-0.466, P=0.020) and L-arginine/ADMA ratio (odds ratio, 1.010; 95% confidence interval, 1.001-1.020, P=0.032) were independent predictors of collateral development. Increased

  19. Asymmetrical reinforcement and Wolbachia infection in Drosophila.

    Directory of Open Access Journals (Sweden)

    John Jaenike


    Full Text Available Reinforcement refers to the evolution of increased mating discrimination against heterospecific individuals in zones of geographic overlap and can be considered a final stage in the speciation process. One the factors that may affect reinforcement is the degree to which hybrid matings result in the permanent loss of genes from a species' gene pool. Matings between females of Drosophila subquinaria and males of D. recens result in high levels of offspring mortality, due to interspecific cytoplasmic incompatibility caused by Wolbachia infection of D. recens. Such hybrid inviability is not manifested in matings between D. recens females and D. subquinaria males. Here we ask whether the asymmetrical hybrid inviability is associated with a corresponding asymmetry in the level of reinforcement. The geographic ranges of D. recens and D. subquinaria were found to overlap across a broad belt of boreal forest in central Canada. Females of D. subquinaria from the zone of sympatry exhibit much stronger levels of discrimination against males of D. recens than do females from allopatric populations. In contrast, such reproductive character displacement is not evident in D. recens, consistent with the expected effects of unidirectional cytoplasmic incompatibility. Furthermore, there is substantial behavioral isolation within D. subquinaria, because females from populations sympatric with D. recens discriminate against allopatric conspecific males, whereas females from populations allopatric with D. recens show no discrimination against any conspecific males. Patterns of general genetic differentiation among populations are not consistent with patterns of behavioral discrimination, which suggests that the behavioral isolation within D. subquinaria results from selection against mating with Wolbachia-infected D. recens. Interspecific cytoplasmic incompatibility may contribute not only to post-mating isolation, an effect already widely recognized, but also to

  20. Success Factors of Asymmetric Connections - Example of Large Slovenian Enterprises

    Directory of Open Access Journals (Sweden)

    Viktor Vračar


    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.

  1. Distribution of quantum Fisher information in asymmetric cloning machines. (United States)

    Xiao, Xing; Yao, Yao; Zhou, Lei-Ming; Wang, Xiaoguang


    An unknown quantum state cannot be copied and broadcast freely due to the no-cloning theorem. Approximate cloning schemes have been proposed to achieve the optimal cloning characterized by the maximal fidelity between the original and its copies. Here, from the perspective of quantum Fisher information (QFI), we investigate the distribution of QFI in asymmetric cloning machines which produce two nonidentical copies. As one might expect, improving the QFI of one copy results in decreasing the QFI of the other copy. It is perhaps also unsurprising that asymmetric phase-covariant cloning outperforms universal cloning in distributing QFI since a priori information of the input state has been utilized. However, interesting results appear when we compare the distributabilities of fidelity (which quantifies the full information of quantum states), and QFI (which only captures the information of relevant parameters) in asymmetric cloning machines. Unlike the results of fidelity, where the distributability of symmetric cloning is always optimal for any d-dimensional cloning, we find that any asymmetric cloning outperforms symmetric cloning on the distribution of QFI for d ≤ 18, whereas some but not all asymmetric cloning strategies could be worse than symmetric ones when d > 18.

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

    Directory of Open Access Journals (Sweden)

    Mohamad Yusoff Alias


    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 (176×144 “Suzie” image. The recursive systematic convolutional (RSC encoder with generator polynomials (1,D3+D2+1/D3+D+1, 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 (1,D3+D2+1/D3+D+1;D3+D2+1/D3+1, 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 N=400, code rate r=1/3 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.

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

    Directory of Open Access Journals (Sweden)

    Siddiqi Mohammad Umar


    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.

  4. Asymmetric MRI Magnet Design Using a Hybrid Numerical Method (United States)

    Zhao, Huawei; Crozier, Stuart; Doddrell, David M.


    This paper describes a hybrid numerical method for the design of asymmetric magnetic resonance imaging magnet systems. The problem is formulated as a field synthesis and the desired current density on the surface of a cylinder is first calculated by solving a Fredholm equation of the first kind. Nonlinear optimization methods are then invoked to fit practical magnet coils to the desired current density. The field calculations are performed using a semi-analytical method. A new type of asymmetric magnet is proposed in this work. The asymmetric MRI magnet allows the diameter spherical imaging volume to be positioned close to one end of the magnet. The main advantages of making the magnet asymmetric include the potential to reduce the perception of claustrophobia for the patient, better access to the patient by attending physicians, and the potential for reduced peripheral nerve stimulation due to the gradient coil configuration. The results highlight that the method can be used to obtain an asymmetric MRI magnet structure and a very homogeneous magnetic field over the central imaging volume in clinical systems of approximately 1.2 m in length. Unshielded designs are the focus of this work. This method is flexible and may be applied to magnets of other geometries.

  5. Transition Metal-Catalyzed Regioselective Asymmetric Mono-hydrogenation of Dienes and Polyenes. (United States)

    Margarita, Cristiana; Rabten, Wangchuk; Andersson, Pher G


    Organic compounds containing multiple C=C bonds are attractive substrates for catalytic asymmetric hydrogenation. The full saturation of prochiral double bonds, controlling the creation of two or more stereocenters in one step, is obviously a remarkable goal. However, another fascinating and useful option is to selectively introduce a new defined stereogenic center, while leaving other double bonds untouched. Thus, the retained functionalities can be further exploited in synthesis. Examples of regio- and enantioselective mono-hydrogenations of polyolefins are highlighted in this Concept article, and are divided according to the nature of the reduced double bond and the transition-metal catalyst used. Alkenes bearing coordinating functional groups are often preferentially hydrogenated by Rh- and Ru-complexes, while the more recently developed Ir-based catalysts promote the selective saturation on alkyl-substituted olefins. Relevant applications of this effective methodology in the synthesis of natural products are included to demonstrate its value in organic synthesis. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Development of the titanium–TADDOLate-catalyzed asymmetric fluorination of β-ketoesters

    Directory of Open Access Journals (Sweden)

    Lukas Hintermann


    Full Text Available Titanium-based Lewis acids catalyze the α-fluorination of β-ketoesters by electrophilic N–F-fluorinating reagents. Asymmetric catalysis with TADDOLato–titanium(IV dichloride (TADDOL = α,α,α',α'-tetraaryl-(1,3-dioxolane-4,5-diyl-dimethanol Lewis acids produces enantiomerically enriched α-fluorinated β-ketoesters in up to 91% enantiomeric excess, with either F–TEDA (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate in acetonitrile solution or NFSI (N-fluorobenzenesulfonimide in dichloromethane solution as fluorinating reagents. The effects of various reaction parameters and of the TADDOL ligand structure on the catalytic activity and enantioselectivity were investigated. The absolute configuration of several fluorination products was assigned through correlation. Evidence for ionization of the catalyst complex by chloride dissociation, followed by generation of titanium β-ketoenolates as key reaction intermediates, was obtained. Based on the experimental findings, a general mechanistic sketch and a steric model of induction are proposed.

  7. Structural determinants of APOBEC3B non-catalytic domain for molecular assembly and catalytic regulation

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Xiao; Yang, Hanjing; Arutiunian, Vagan; Fang, Yao; Besse, Guillaume; Morimoto, Cherie; Zirkle, Brett; Chen, Xiaojiang S. (USC)


    The catalytic activity of human cytidine deaminase APOBEC3B (A3B) has been correlated with kataegic mutational patterns within multiple cancer types. The molecular basis of how the N-terminal non-catalytic CD1 regulates the catalytic activity and consequently, biological function of A3B remains relatively unknown. Here, we report the crystal structure of a soluble human A3B-CD1 variant and delineate several structural elements of CD1 involved in molecular assembly, nucleic acid interactions and catalytic regulation of A3B. We show that (i) A3B expressed in human cells exists in hypoactive high-molecular-weight (HMW) complexes, which can be activated without apparent dissociation into low-molecular-weight (LMW) species after RNase A treatment. (ii) Multiple surface hydrophobic residues of CD1 mediate the HMW complex assembly and affect the catalytic activity, including one tryptophan residue W127 that likely acts through regulating nucleic acid binding. (iii) One of the highly positively charged surfaces on CD1 is involved in RNA-dependent attenuation of A3B catalysis. (iv) Surface hydrophobic residues of CD1 are involved in heterogeneous nuclear ribonucleoproteins (hnRNPs) binding to A3B. The structural and biochemical insights described here suggest that unique structural features on CD1 regulate the molecular assembly and catalytic activity of A3B through distinct mechanisms.

  8. Tandem reactions in self-sorted catalytic molecular hydrogels

    NARCIS (Netherlands)

    Singh, N.; Zhang, K.; Angulo-Pachón, C.A.; Mendez Sevillano, D.; van Esch, J.H.; Escuder, B.


    By equipping mutually incompatible carboxylic acid and proline catalytic groups with different self-assembling motives we have achieved self-sorting of the resulting catalytic gelators, namely SucVal8 and ProValDoc, into different supramolecular fibers, thus preventing the acidic and basic catalytic


    African Journals Online (AJOL)

    indicator reaction for the kinetic-catalytic determination of Ru(III) is explored. In this communication, we report a kinetic-catalytic method for determination Ru(III), using it's selective catalytic efficiency to catalyse the oxidation of Nile blue by acidic chlorite. EXPERIMENTAL. Reagents. Sodium chlorite (BDH) was recrystallized ...

  10. Six transformer based asymmetrical embedded Z-source inverters

    DEFF Research Database (Denmark)

    Wei, Mo; Poh Chiang, Loh; Chi, Jin


    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.......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...

  11. Solitary waves in asymmetric electron-positron-ion plasmas (United States)

    Lu, Ding; Li, Zi-Liang; Xie, Bai-Song


    > By solving the coupled equations of the electromagnetic field and electrostatic potential, we investigate solitary waves in an asymmetric electron-positron plasma and/or electron-positron-ion plasmas with delicate features. It is found that the solutions of the coupled equations can capture multipeak structures of solitary waves in the case of cold plasma, which are left out by using the long-wavelength approximation. By considering the effect of ion motion with respect to non-relativistic and ultra-relativistic temperature plasmas, we find that the ions' mobility can lead to larger-amplitude solitary waves; especially, this becomes more obvious for a high-temperature plasma. The effects of asymmetric temperature between electrons and positrons and the ion fraction on the solitary waves are also studied and presented. It is shown that the amplitudes of solitary waves decrease with positron temperature in asymmetric temperature electron-positron plasmas and decrease also with ion concentration.

  12. Complete polarimetry on the asymmetric transmission through subwavelength hole arrays. (United States)

    Arteaga, Oriol; Maoz, Ben M; Nichols, Shane; Markovich, Gil; Kahr, Bart


    Dissymmetric, periodically nanostructured metal films can show non-reciprocal transmission of polarized light, in apparent violation of the Lorentz reciprocity theorem. The wave vector dependence of the extraordinary optical transmission in gold films with square and oblique subwavelength hole arrays was examined for the full range of polarized light input states. In normal incidence, the oblique lattice, in contrast to square lattice, showed strong asymmetric, non-reciprocal transmission of circularly polarized light. By analyzing the polarization of the input and the output with a complete Mueller matrix polarimeter the mechanisms that permits asymmetric transmission while preserving the requirement of electromagnetic reciprocity is revealed: the coupling of the linear anisotropies induced by misaligned surface plasmons in the film. The square lattice also shows asymmetric transmission at non-normal incidence, whenever the plane of incidence does not coincide with a mirror line.

  13. Left-Right Asymmetrical Development of the Proepicardium

    Directory of Open Access Journals (Sweden)

    Jan Schlueter


    Full Text Available The proepicardium (PE is a cluster of cells that forms on the cardiac inflow tract and gives rise to the epicardium and connective tissue and largely contributes to the coronary vasculature. In many vertebrates, the PE undergoes left-right asymmetrical development. While PE cells and marker genes can be initially found on both sides, only the right-sided PE will fully develop and ultimately deliver cells to the heart. Several signalling inputs, like FGF and BMP signals, are involved in PE induction in the lateral plate mesoderm, as well as during inflow tract formation and, also, control asymmetric PE development. These signalling events will be put into the context of embryonic left-right asymmetry determination. Finally, it will be discussed whether PE development may serve as a readout for asymmetric inflow tract morphogenesis.

  14. Asymmetric nanoparticle may go "active" at room temperature (United States)

    Sheng, Nan; Tu, YuSong; Guo, Pan; Wan, RongZheng; Wang, ZuoWei; Fang, HaiPing


    Using molecular dynamics simulations, we show that an asymmetrically shaped nanoparticle in dilute solution possesses a spontaneously curved trajectory within a finite time interval, instead of the generally expected random walk. This unexpected dynamic behavior has a similarity to that of active matters, such as swimming bacteria, cells, or even fish, but is of a different physical origin. The key to the curved trajectory lies in the non-zero resultant force originated from the imbalance of the collision forces acted by surrounding solvent molecules on the asymmetrically shaped nanoparticle during its orientation regulation. Theoretical formulae based on microscopic observations have been derived to describe this non-zero force and the resulting motion of the asymmetrically shaped nanoparticle.

  15. Abel inversion of asymmetric plasma density profile at Aditya tokamak (United States)

    Joshi, N. Y.; Atrey, P. K.; Pathak, S. K.


    In Aditya tokamak, at Institute for Plasma Research, till now, multi-channel microwave interferometer system is used to measure the cord averaged plasma density at predefined radial position. An inversion code is developed to determine the local density profile from the chord average density measurement of radially asymmetric plasma. The radial density profile is interpolated using Spline interpolation analytical technique for symmetric plasma density profile. Code implements the Slice and Stack method to determine localized density from asymmetric averaged plasma density measurement from interferometer. Inverted results are tested with various monotonically varying asymmetric radial density profiles of the plasma shots. It also provides the poloidal picture of plasma density distribution with circular constant density surfaces. Localized density measurements, which is very important for successful operation of tokamak, is in agreement with observation of other diagnostics.

  16. Asymmetric microscope; Fusho no kenbisho {exclamation_point}?

    Energy Technology Data Exchange (ETDEWEB)

    Inoue, Tadashi. [Tokyo Institute of Technology, Tokyo (Japan)


    It is difficult for a conventional optical analysis means to determine the configuration of a substance with an ultra low optical purity. Recently, an asymmetric microscope has been reported as a new concept for solving the above-mentioned problem. Specifically, a product with slight asymmetry is obtained by using the substance with an ultra low optical purity as the chiral initiation, and then the asymmetry of the product is amplified dramatically due to the asymmetric autocatalysis, thus obtaining a product having a high optical purity. A new means is to determine the configuration of the original substance having the low optical purity from the configuration of the substance having the high optical purity. According to this method, the chirality of the substance having the low optical purity is transcribed to alkanol, and the chirality is amplified due to the asymmetric autocatalysis, thus the absolute configuration of the original compound can be determined from the absolute configuration of the final product. (NEDO)

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


    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.

  18. Efficient Algorithms with Asymmetric Read and Write Costs


    Blelloch, Guy E.; Fineman, Jeremy T.; Gibbons, Phillip B.; Gu, Yan; Shun, Julian


    In several emerging technologies for computer memory (main memory), the cost of reading is significantly cheaper than the cost of writing. Such asymmetry in memory costs poses a fundamentally different model from the RAM for algorithm design. In this paper we study lower and upper bounds for various problems under such asymmetric read and write costs. We consider both the case in which all but O(1) memory has asymmetric cost, and the case of a small cache of symmetric memory. We model both ...

  19. Asymmetric Cerebral Lesion Pattern in X-linked Adrenoleukodystrophy

    Directory of Open Access Journals (Sweden)

    Shuang Wang


    Full Text Available X-linked adrenoleukodystrophy (X-ALD is an inherited disease caused by peroxisomal dysfunction. X-ALD usually involves the cerebral white matter in an approximately symmetric way. We report a 10-year-old boy with the cerebral form of X-ALD who presented with cognitive impairment and left spastic hemiparesis. Brain magnetic resonance imaging (MRI showed asymmetric lesions, and the lesions in the right hemisphere were predominant. In the late stage of the disease, bilateral limbs were involved. The cerebral lesions enlarged and appeared approximately symmetric on MRI. The purpose of our report is to highlight asymmetric demyelination in initial presentation of X-ALD.

  20. Asymptotic behavior of observables in the asymmetric quantum Rabi model (United States)

    Semple, J.; Kollar, M.


    The asymmetric quantum Rabi model with broken parity invariance shows spectral degeneracies in the integer case, that is when the asymmetry parameter equals an integer multiple of half the oscillator frequency, thus hinting at a hidden symmetry and accompanying integrability of the model. We study the expectation values of spin observables for each eigenstate and observe characteristic differences between the integer and noninteger cases for the asymptotics in the deep strong coupling regime, which can be understood from a perturbative expansion in the qubit splitting. We also construct a parent Hamiltonian whose exact eigenstates possess the same symmetries as the perturbative eigenstates of the asymmetric quantum Rabi model in the integer case.

  1. Recent advances in copper-catalyzed asymmetric coupling reactions

    Directory of Open Access Journals (Sweden)

    Fengtao Zhou


    Full Text Available Copper-catalyzed (or -mediated asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C–C, C–N, C–O and other carbon–heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C–C and carbon–heteroatom bonds.

  2. Data analysis of asymmetric structures advanced approaches in computational statistics

    CERN Document Server

    Saito, Takayuki


    Data Analysis of Asymmetric Structures provides a comprehensive presentation of a variety of models and theories for the analysis of asymmetry and its applications and provides a wealth of new approaches in every section. It meets both the practical and theoretical needs of research professionals across a wide range of disciplines and  considers data analysis in fields such as psychology, sociology, social science, ecology, and marketing. In seven comprehensive chapters this guide details theories, methods, and models for the analysis of asymmetric structures in a variety of disciplines and presents future opportunities and challenges affecting research developments and business applications.

  3. Finite stage asymmetric repeated games: Both players' viewpoints

    KAUST Repository

    Li, Lichun


    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.

  4. Ratchet effect of the domain wall by asymmetric magnetostatic potentials (United States)

    Piao, Hong-Guang; Choi, Hyeok-Cheol; Shim, Je-Ho; Kim, Dong-Hyun; You, Chun-Yeol


    We investigate a ratchet effect of magnetic domain wall motion in a ferromagnetic nanowire under AC magnetic fields using micromagnetic simulation. The ratchet effect for a transverse domain wall is achieved using an asymmetric magnetic potential generated by stray fields from non-contact trapezoidal ferromagnetic stubs near the straight nanowire. The ratchet phenomenon has been examined with various combinations of amplitude and frequency of the driving AC field. Interestingly, we find that the domain wall propagates along a preferential direction by the diode-like ratchet effect under AC field. The propagation of the domain wall strongly depends on the profile of the asymmetrical magnetic potentials and the driving AC field characteristics.

  5. On the topology defined by Thurston's asymmetric metric

    DEFF Research Database (Denmark)

    Papadopoulos, Athanase; Theret, Guillaume


    We establish some properties of Thurston's asymmetric metric L on the Teichmüller space of a surface of genus with punctures and with negative Euler characteristic. We study convergence of sequences of elements in in the sense of L, as well as sequences that tend to infinity in . We show...... that the topology that the asymmetric metric L induces on Teichmüller space is the same as the usual topology. Furthermore, we show that L satisfies the axioms of a (not necessarily symmetric) metric in the sense of Busemann and conclude that L is complete in the sense of Busemann....

  6. Role of Asymmetric Clusters in Desynchronization of Coherent Motion

    DEFF Research Database (Denmark)

    Popovych, O.; Maistrenko, Y.; Mosekilde, Erik


    The transition from full synchronization (coherent motion) to two-cluster dynamics is studied for a system of N globally coupled logistic maps. When increasing the nonlinearity parameter of the individual map, new periodic and strongly asymmetric two-cluster states are found to emerge in the same...... order as the periodic windows arise in the logistic map. These strongly asymmetric two-cluster states are generally first to stabilize when reducing the coupling strength. Similar phenomena are also observed for a system of globally coupled Henon maps....

  7. Climate agreements under limited participation, asymmetric information and market imperfections

    Energy Technology Data Exchange (ETDEWEB)

    Hagem, Cathrine


    This thesis relates to climate agreements and cost efficiency by analysing the formation of a system of quota leading to distributed discharge of emissions between countries. Main fields concerned are the greenhouse effect, the political process, efficient and cost-effective climate agreements, and climate agreements under limited participation, asymmetric information and market imperfections covering fields like limited participation in climate agreements, limited participation and indirect impact on non-participating countries` emissions, limited participation and direct impact on non-participating countries` emissions under asymmetric information, and non-competitive market for tradeable quotas. 166 refs., 7 tabs.

  8. Asymmetric salivary gland uptake: Potential pitfall following radioiodide therapy

    Energy Technology Data Exchange (ETDEWEB)

    Slavin, J.D. Jr.; Mack, J.M.; Spencer, R.P.


    A 67-year old woman, with prior radioiodide (/sup 131/I) therapy for differentiated thyroid carcinoma, had a follow-up scan that revealed asymmetric accumulation in the left upper neck and cheek regions. This resembled functioning metastatic tissue. An immediate /sup 99m/Tc-pertechnetate image demonstrated accumulation in the same areas. This corresponded to activity in the left submandibular gland and parotid. Hence, asymmetric salivary gland uptake was mimicking functional thyroid metastases. Possible causes of the disparate salivary gland function were discussed.

  9. Structure of the catalytic chain of Methanococcus jannaschii aspartate transcarbamoylase in a hexagonal crystal form: Insights into the path of carbamoyl phosphate to the active site of the enzyme

    Energy Technology Data Exchange (ETDEWEB)

    Vitali J.; Soares A.; Singh, A. K.; Colaneri, M. J.


    Crystals of the catalytic chain of Methanococcus jannaschii aspartate transcarbamoylase (ATCase) grew in the presence of the regulatory chain in the hexagonal space group P6{sub 3}22, with one monomer per asymmetric unit. This is the first time that crystals with only one monomer in the asymmetric unit have been obtained; all known structures of the catalytic subunit contain several crystallographically independent monomers. The symmetry-related chains form the staggered dimer of trimers observed in the other known structures of the catalytic subunit. The central channel of the catalytic subunit contains a sulfate ion and a K{sup +} ion as well as a glycerol molecule at its entrance. It is possible that it is involved in channeling carbamoyl phosphate (CP) to the active site of the enzyme. A second sulfate ion near Arg164 is near the second CP position in the wild-type Escherichia coli ATCase structure complexed with CP. It is suggested that this position may also be in the path that CP takes when binding to the active site in a partial diffusion process at 310 K. Additional biochemical studies of carbamoylation and the molecular organization of this enzyme in M. jannaschii will provide further insight into these points.

  10. Allenes in Asymmetric Catalysis. Asymmetric Ring-Opening of Meso-Epoxides Catalyzed by Allene-Containing Phosphine Oxides (United States)

    Pu, Xiaotao; Qi, Xiangbing; Ready, Joseph M.


    Unsymmetrically substituted allenes (1,2 dienes) are inherently chiral and can be prepared in optically pure form. Nonetheless, to date the allene framework has not been incorporated into ligands for asymmetric catalysis. Since allenes project functionality differently than either tetrahedral carbon or chiral biaryls, they may create complementary chiral environments. This study demonstrates that optically active C2 symmetric allene-containing bisphosphine oxides can catalyze the addition of SiCl4 to meso epoxides with high enantioselectivity. The epoxide-opening likely involves generation of a Lewis acidic, cationic (bisphosphine oxide)SiCl3 complex. The fact that high asymmetric induction is observed suggests that allenes may represent a new platform for the development of ligands and catalysts for asymmetric synthesis. PMID:19722613

  11. Catalytic site interactions in yeast OMP synthase

    DEFF Research Database (Denmark)

    Hansen, Michael Riis; Barr, Eric W.; Jensen, Kaj Frank


    The enigmatic kinetics, half-of-the-sites binding, and structural asymmetry of the homodimeric microbial OMP synthases (orotate phosphoribosyltransferase, EC have been proposed to result from an alternating site mechanism in these domain-swapped enzymes [R.W. McClard et al., Biochemistry...... and ablated ability to bind PRPP, complemented to produce a heterodimer with a single fully functional active site showing intersecting initial velocity plots. Equilibrium binding of PRPP and orotidine 5'-monophosphate showed a single class of two binding sites per dimer in WT and K106S enzymes. Evidence here...... shows that the enzyme does not follow half-of-the-sites cooperativity; that interplay between catalytic sites is not an essential feature of the catalytic mechanism; and that parallel lines in steady-state kinetics probably arise from tight substrate binding....

  12. Mutational analysis of a ras catalytic domain

    DEFF Research Database (Denmark)

    Willumsen, B M; Papageorge, A G; Kung, H F


    transformation of NIH 3T3 cells with approximately the same efficiency as the wild-type v-rasH gene to those that failed to induce any detectable morphologic changes. Correlation of transforming activity with the location of the mutations enabled us to identify three nonoverlapping segments within the catalytic......We used linker insertion-deletion mutagenesis to study the catalytic domain of the Harvey murine sarcoma virus v-rasH transforming protein, which is closely related to the cellular rasH protein. The mutants displayed a wide range of in vitro biological activity, from those that induced focal...... localization. We speculate that this latter region interacts with the putative cellular target of ras. The results suggest that transforming ras proteins require membrane localization, guanosine nucleotide binding, and an additional undefined function that may represent interaction with their target....

  13. Catalytic combustion of coal-derived liquids (United States)

    Bulzan, D. L.; Tacina, R. R.


    A noble metal catalytic reactor was tested with three grades of SRC 2 coal derived liquids, naphtha, middle distillate, and a blend of three parts middle distillate to one part heavy distillate. A petroleum derived number 2 diesel fuel was also tested to provide a direct comparison. The catalytic reactor was tested at inlet temperatures from 600 to 800 K, reference velocities from 10 to 20 m/s, lean fuel air ratios, and a pressure of 3 x 10 to the 5th power Pa. Compared to the diesel, the naphtha gave slightly better combustion efficiency, the middle distillate was almost identical, and the middle heavy blend was slightly poorer. The coal derived liquid fuels contained from 0.58 to 0.95 percent nitrogen by weight. Conversion of fuel nitrogen to NOx was approximately 75 percent for all three grades of the coal derived liquids.


    Energy Technology Data Exchange (ETDEWEB)

    M.S. El Ouchdi, L. Cherif, R. Bachir, A. Choukchou-Braham, S. Merad-Bedrane [Laboratory of Catalysis and Synthesis in Organic Chemistry, University of Tlemcen, Chemistry Department, Tiemcen (Algeria)


    One of the greatest revolutions in the 20th century is that of transport. Inventions of cars, trucks, and airplanes have created a new world that has become increasingly dependent on combustion of hydrocarbon fuels such as gasoline, diesel fuel, and jet fuel. Major environmental global problems are due to emissions of pollutants from fuels combustion, such as NOx, SOx, particulate matter and greenhouse gases (CO2 , CH4 , etc.). The present work is devoted to the study of ethanol catalytic steam reforming. The challenge is a high yield in hydrogen and a high selectivity towards CO2 . The reaction is classically carried out over transition metal catalysts supported on Al2O3, MgO, ZnO and SiO2. Our innovation consists in using mesoporous materials such as SBA-15, Al-SBA-15, CMK3 and mesoporous Alumina known for very interesting and large catalytic properties as supports for our metal catalysts. Cupper and nickel were used as active metal phase. The interest of our work is to obtain high activities under mild conditions. In fact, catalytic tests were carried out in gas phase at 300 C and atmospheric pressure. Ethanol and water were automatically injected with a constant velocity of 0.033 cm3 min-1 and a molar ratio ethanol/water = 1/3. Such operating conditions could be easily reproduced on-board. Catalysts were fully characterized using XRD, EM, TPR and metal loading analysis. Influence of the nature and the structure of the mesoporous support, the nature of the metal, the preparation way, the metal loading and catalysts pre-treatment was checked. A correlation between the materials' properties and catalytic activities will be suggested. All these results will be widely discussed during the presentation.

  15. CO2 Activation over Catalytic Surfaces. (United States)

    Álvarez, Andrea; Borges, Marta; Corral-Pérez, Juan José; Olcina, Joan Giner; Hu, Lingjun; Cornu, Damien; Huang, Rui; Stoian, Dragos; Urakawa, Atsushi


    This article describes the main strategies to activate and convert carbon dioxide (CO2 ) into valuable chemicals over catalytic surfaces. Coherent elements such as common intermediates are identified in the different strategies and concisely discussed based on the reactivity of CO2 with the aim to understand the decisive factors for selective and efficient CO2 conversion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Zeolitic catalytic conversion of alochols to hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin


    A method for converting an alcohol to a hydrocarbon, the method comprising contacting said alcohol with a metal-loaded zeolite catalyst at a temperature of at least C. and up to C., wherein said alcohol can be produced by a fermentation process, said metal is a positively-charged metal ion, and said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said hydrocarbon.

  17. Supercritical Catalytic Cracking of Hydrocarbon Feeds Insight (United States)


    collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources ...failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE...and parasitic catalytic cracking pathways. Synthetic methods to produce mordenite framework inverted (MFI) crystals with dimensions as large as 150

  18. Control of a catalytic fluid cracker

    Energy Technology Data Exchange (ETDEWEB)

    Arbel, A.; Huang, Z.; Rinard, I.; Shinnar, R.


    Control offers an important tool for savings in refineries, mainly by integration of process models into on-line control. This paper is part of a research effort to better understand problems of partial control; control of a Fluid Catalytic Cracker (FCC) is used as example. Goal is to understand better the control problems of an FCC in context of model based control of a refinery, and to understand the general problem of designing partial control systems.

  19. Catalytic fast pyrolysis of lignocellulosic biomass. (United States)

    Liu, Changjun; Wang, Huamin; Karim, Ayman M; Sun, Junming; Wang, Yong


    Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectively convert lignocellulose into a liquid fuel-bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating value, high corrosiveness, high viscosity, and instability; they also greatly limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.

  20. Method to produce catalytically active nanocomposite coatings (United States)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat


    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  1. Materials for High-Temperature Catalytic Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Ersson, Anders


    Catalytic combustion is an environmentally friendly technique to combust fuels in e.g. gas turbines. Introducing a catalyst into the combustion chamber of a gas turbine allows combustion outside the normal flammability limits. Hence, the adiabatic flame temperature may be lowered below the threshold temperature for thermal NO{sub X} formation while maintaining a stable combustion. However, several challenges are connected to the application of catalytic combustion in gas turbines. The first part of this thesis reviews the use of catalytic combustion in gas turbines. The influence of the fuel has been studied and compared over different catalyst materials. The material section is divided into two parts. The first concerns bimetallic palladium catalysts. These catalysts showed a more stable activity compared to their pure palladium counterparts for methane combustion. This was verified both by using an annular reactor at ambient pressure and a pilot-scale reactor at elevated pressures and flows closely resembling the ones found in a gas turbine combustor. The second part concerns high-temperature materials, which may be used either as active or washcoat materials. A novel group of materials for catalysis, i.e. garnets, has been synthesised and tested in combustion of methane, a low-heating value gas and diesel fuel. The garnets showed some interesting abilities especially for combustion of low-heating value, LHV, gas. Two other materials were also studied, i.e. spinels and hexa aluminates, both showed very promising thermal stability and the substituted hexa aluminates also showed a good catalytic activity. Finally, deactivation of the catalyst materials was studied. In this part the sulphur poisoning of palladium, platinum and the above-mentioned complex metal oxides has been studied for combustion of a LHV gas. Platinum and surprisingly the garnet were least deactivated. Palladium was severely affected for methane combustion while the other washcoat materials were

  2. Method to produce catalytically active nanocomposite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat


    A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

  3. Preface: Challenges for Catalytic Exhaust Aftertreatment

    Energy Technology Data Exchange (ETDEWEB)

    Nova, Isabella; Epling, Bill; Peden, Charles HF


    This special issue of Catalysis Today continues the tradition established since the 18th NAM in Cancun, 2003, of publishing the highlights coming from these catalytic after-treatment technologies sessions, where this volume contains 18 papers based on oral and poster presentations of the 23rd NAM, 2013. The guest editors would like to thank all of the catalyst scientists and engineers who presented in the "Emission control" sessions, and especially the authors who contributed to this special issue of Catalysis Today.

  4. Probing catalytic rate enhancement during intramembrane proteolysis. (United States)

    Arutyunova, Elena; Smithers, Cameron C; Corradi, Valentina; Espiritu, Adam C; Young, Howard S; Tieleman, D Peter; Lemieux, M Joanne


    Rhomboids are ubiquitous intramembrane serine proteases involved in various signaling pathways. While the high-resolution structures of the Escherichia coli rhomboid GlpG with various inhibitors revealed an active site comprised of a serine-histidine dyad and an extensive oxyanion hole, the molecular details of rhomboid catalysis were unclear because substrates are unknown for most of the family members. Here we used the only known physiological pair of AarA rhomboid with its psTatA substrate to decipher the contribution of catalytically important residues to the reaction rate enhancement. An MD-refined homology model of AarA was used to identify residues important for catalysis. We demonstrated that the AarA active site geometry is strict and intolerant to alterations. We probed the roles of H83 and N87 oxyanion hole residues and determined that substitution of H83 either abolished AarA activity or reduced the transition state stabilization energy (ΔΔG‡) by 3.1 kcal/mol; substitution of N87 decreased ΔΔG‡ by 1.6-3.9 kcal/mol. Substitution M154, a residue conserved in most rhomboids that stabilizes the catalytic general base, to tyrosine, provided insight into the mechanism of nucleophile generation for the catalytic dyad. This study provides a quantitative evaluation of the role of several residues important for hydrolytic efficiency and oxyanion stabilization during intramembrane proteolysis.

  5. Catalytic pyrolysis of olive mill wastewater sludge (United States)

    Abdellaoui, Hamza

    From 2008 to 2013, an average of 2,821.4 kilotons/year of olive oil were produced around the world. The waste product of the olive mill industry consists of solid residue (pomace) and wastewater (OMW). Annually, around 30 million m3 of OMW are produced in the Mediterranean area, 700,000 m3 year?1 in Tunisia alone. OMW is an aqueous effluent characterized by an offensive smell and high organic matter content, including high molecular weight phenolic compounds and long-chain fatty acids. These compounds are highly toxic to micro-organisms and plants, which makes the OMW a serious threat to the environment if not managed properly. The OMW is disposed of in open air evaporation ponds. After evaporation of most of the water, OMWS is left in the bottom of the ponds. In this thesis, the effort has been made to evaluate the catalytic pyrolysis process as a technology to valorize the OMWS. The first section of this research showed that 41.12 wt. % of the OMWS is mostly lipids, which are a good source of energy. The second section proved that catalytic pyrolysis of the OMWS over red mud and HZSM-5 can produce green diesel, and 450 °C is the optimal reaction temperature to maximize the organic yields. The last section revealed that the HSF was behind the good fuel-like properties of the OMWS catalytic oils, whereas the SR hindered the bio-oil yields and quality.

  6. Demonstration of catalytic combustion with residual fuel (United States)

    Dodds, W. J.; Ekstedt, E. E.


    An experimental program was conducted to demonstrate catalytic combustion of a residual fuel oil. Three catalytic reactors, including a baseline configuration and two backup configurations based on baseline test results, were operated on No. 6 fuel oil. All reactors were multielement configurations consisting of ceramic honeycomb catalyzed with palladium on stabilized alumina. Stable operation on residual oil was demonstrated with the baseline configuration at a reactor inlet temperature of about 825 K (1025 F). At low inlet temperature, operation was precluded by apparent plugging of the catalytic reactor with residual oil. Reduced plugging tendency was demonstrated in the backup reactors by increasing the size of the catalyst channels at the reactor inlet, but plugging still occurred at inlet temperature below 725 K (845 F). Operation at the original design inlet temperature of 589 K (600 F) could not be demonstrated. Combustion efficiency above 99.5% was obtained with less than 5% reactor pressure drop. Thermally formed NO sub x levels were very low (less than 0.5 g NO2/kg fuel) but nearly 100% conversion of fuel-bound nitrogen to NO sub x was observed.

  7. Asymmetric activation spreading in the multiplication associative network due to asymmetric overlap between numerosities semantic representations? (United States)

    Didino, Daniele; Knops, André; Vespignani, Francesco; Kornpetpanee, Suchada


    Simple multiplication facts are thought to be organised in a network structure in which problems and solutions are associated. Converging evidence suggests that the ability for solving symbolic arithmetic problems is based on an approximate number system (ANS). Most theoretical stances concerning the metric underlying the ANS converge on the assumption that the representational overlap between two adjacent numbers increases as the numerical magnitude of the numbers increases. Given a number N, the overlap between N and N+1 is larger than the overlap between N and N-1. Here, we test whether this asymmetric overlap influences the activation spreading within the multiplication associative network (MAN). When verifying simple multiplication problems such as 8×4 participants were slower in rejecting false but related outcomes that were larger than the actual outcome (e.g., 8×4=36) than rejecting smaller related outcomes (e.g., 8×4=28), despite comparable numerical distance from the correct result (here: 4). This effect was absent for outcomes which are not part of either operands table (e.g., 8×4=35). These results suggest that the metric of the ANS influences the activation spreading within the MAN, further substantiating the notion that symbolic arithmetic is grounded in the ANS. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. An Asymmetrical Space Vector Method for Single Phase Induction Motor

    DEFF Research Database (Denmark)

    Cui, Yuanhai; Blaabjerg, Frede; Andersen, Gert Karmisholt


    the motor torque performance is not good enough. This paper addresses a new control method, an asymmetrical space vector method with PWM modulation, also a three-phase inverter is used for the main winding and the auxiliary winding. This method with PWM modulation is implemented to control the motor speed...

  9. Asymmetric Threat Assessment Using Electro-Optical Image Systems

    NARCIS (Netherlands)

    Schwering, P.B.W.; Schutte, K.


    Asymmetric threat assessment from military platforms, including early detection and classification by electro-optical means, is a complicated matter. These threats can be for instance explosives-packed rubber boats, minecarrying swimmers and divers in a marine environment or terrorists, improvised

  10. Efficient asymmetric Baeyer-Villiger oxidation of prochiral ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 124; Issue 4. Efficient asymmetric Baeyer-Villiger oxidation of prochiral cyclobutanones using new polymer-supported and unsupported chiral co(salen) complexes. Reza Sandaroos Mohammad Taghi Goldani Saman Damavandi Ali Mohammadi. Volume 124 Issue 4 ...

  11. Attempt to accelerate asymmetric species with unequal frequencies in RHIC

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C. [Brookhaven National Lab. (BNL), Upton, NY (United States); Luo, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Marusic, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Minty, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Robert-Demolaize, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Smith, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Mernick, K. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hayes, T. [Brookhaven National Lab. (BNL), Upton, NY (United States); Severino, F. [Brookhaven National Lab. (BNL), Upton, NY (United States)


    This report summarizes the beam studies on accelerating asymmetric beams with unequal frequencies, during the proton-Gold/Aluminum run in 2015. The experiment failed due to modulated beam-beam effects even though the beams were separated by at least 15 mm.

  12. Novel Cinchona derived organocatalysts: new asymmetric transformations and catalysis

    NARCIS (Netherlands)

    Breman, A.C.


    Cinchona alkaloids have a long history as being a powerful medicine against malaria. Since a relative short period (about 50 years) chemist have also used these alkaloids as chiral catalyst for a wide variety of asymmetric transformations. Especially since the beginning of this century, when strong

  13. Unexpected phase behavior of an asymmetric diblock copolymer

    DEFF Research Database (Denmark)

    Papadakis, Christine Maria; Almdal, Kristoffer; Mortensen, Kell


    We report on measurements of the transmitted depolarized light intensity and on small-angle neutron scattering (SANS) measurements on a compositionally asymmetric poly(ethylene propylene)-poly(dimethylsiloxane) diblock copolymer studied in the bulk. SANS measurements were made both on isotropic a...

  14. Welfare-Improving Asymmetric Information in Dynamic Insurance Markets. (United States)

    de Garidel-Thoron, Thomas


    This article presents a two-period asymmetric learning model of insurance markets. When information about past accidents is not shared by insurers, asymmetries of information develop through time. Equilibrium contracts exist, are payoff unique, and display a realistic bonus-malus pattern. Eliminating asymmetries through information sharing is…

  15. Asymmetric total synthesis of (-)-azaspirene, a novel angiogenesis inhibitor. (United States)

    Hayashi, Yujiro; Shoji, Mitsuru; Yamaguchi, Junichiro; Sato, Kenji; Yamaguchi, Shinpei; Mukaiyama, Takasuke; Sakai, Ken; Asami, Yukihiro; Kakeya, Hideaki; Osada, Hiroyuki


    The asymmetric total synthesis of (-)-azaspirene, an angiogenesis inhibitor, has been accomplished, establishing its absolute stereochemistry. The key steps are a MgBr2.OEt2-mediated, diastereoselective Mukaiyama aldol reaction, a NaH-promoted, intramolecular cyclization of an alkynylamide, and the aldol reaction of a ketone containing functionalized gamma-lactam moiety without protection of tert-alcohol and amide functionalities.

  16. The Asymmetric Simple Exclusion Process: An Exactly Solvable ...

    Indian Academy of Sciences (India)

    Arvind Ayyer, Indian Institute of Science


    Jun 30, 2017 ... Introduction. Multispecies ASEP. Affine Weyl Groups. Table of Contents. 1 Introduction. Motivation. Toy Model. 2 Multispecies ASEP. 3 Affine Weyl Groups. Arvind Ayyer, IISc. 28th Mid Year Meeting Faculty Hall, Indian Institute of Science. Asymmetric Simple Exclusion Process ...

  17. Pulse generation and compression using an asymmetrical porous ...

    Indian Academy of Sciences (India)

    We propose an asymmetrical Mach–Zehnder interferometer (MZI) for efficient pulse generation and compression using porous silicon (PS) waveguide, fibre delay line and couplers. We show a pulse compression of about 0.4 ns at the output port with third-order super-Gaussian input pulse in ∼2 ns time duration and ∼40.3 ...

  18. Linguistic Correlates of Asymmetric Motor Symptom Severity in Parkinson's Disease (United States)

    Holtgraves, Thomas; McNamara, Patrick; Cappaert, Kevin; Durso, Raymond


    Asymmetric motor severity is common in Parkinson's Disease (PD) and provides a method for examining the neurobiologic mechanisms underlying cognitive and linguistic deficits associated with the disorder. In the present research, PD participants (N = 31) were assessed in terms of the asymmetry of their motor symptoms. Interviews with the…

  19. Current Topics in the Asymmetric Transfer Hydrogenation of Imines

    Czech Academy of Sciences Publication Activity Database

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


    Roč. 109, č. 7 (2015), s. 492-498 ISSN 0009-2770 R&D Projects: GA ČR GAP106/12/1276; GA MŠk(CZ) LO1509 Institutional support: RVO:61388971 Keywords : asymmetric transfer hydrogenation * ruthenium * isoquinoline Subject RIV: EE - Microbiology, Virology Impact factor: 0.279, year: 2015

  20. The SU(2)-Higgs model on asymmetric lattices

    CERN Document Server

    Csikor, Ferenc


    We calculate the {\\cal O}(g^2,\\lambda) corrections to the coupling anisotropies of the SU(2)-Higgs model on lattices with asymmetric lattice spacings. These corrections are obtained by a one-loop calculation requiring the rotational invariance of the gauge- and Higgs-boson propagators in the continuum limit.

  1. Physics at a 10{sup 36} Asymmetric B Factory

    Energy Technology Data Exchange (ETDEWEB)

    Roodman, Aaron


    The physics opportunities at an asymmetric B Factory operating at the unprecedented luminosity of 10{sup 36} cm{sup -2}s{sup -1} are unique and attractive. The accelerator appears to be practical and the challenges of performing a sensitive experiment in this environment can be met.

  2. Luminosity lifetime at an asymmetric e sup + e sup - collider

    Energy Technology Data Exchange (ETDEWEB)

    Porter, F.C. (California Inst. of Tech., Pasadena (USA). Lauritsen Lab. of High Energy Physics)


    The dependence of the luminosity on time is discussed for an asymmetric e{sup +}e{sup -} storage ring collider, with emphasis on single-particle scattering mechanisms for beam loss. The 'optimal' filling strategy and average luminosity obtainable are also reviewed. (orig.).

  3. An EMG technique for measuring spinal loading during asymmetric lifting

    NARCIS (Netherlands)

    Dolan, P.; Kingma, I.; De Looze, M. P.; Van Dieen, J. H.; Toussaint, H. M.; Baten, C.T.M.; Adams, M.A.


    Objective. To compare two methods of calibrating the erector spinae electromyographic signal against moment generation in order to predict extensor moments during asymmetric lifting tasks, and to compare the predicted moments with those obtained using a linked-segment model. Methods. Eight men

  4. Bound states in a hyperbolic asymmetric double-well

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, R. R., E-mail: [Physics Department, De La Salle University, 2401 Taft Avenue, Manila (Philippines)


    We report a new class of hyperbolic asymmetric double-well whose bound state wavefunctions can be expressed in terms of confluent Heun functions. An analytic procedure is used to obtain the energy eigenvalues and the criterion for the potential to support bound states is discussed.

  5. Plasmonic Terahertz Amplification in Graphene-Based Asymmetric Hyperbolic Metamaterial

    Directory of Open Access Journals (Sweden)

    Igor Nefedov


    Full Text Available We propose and theoretically explore terahertz amplification, based on stimulated generation of plasmons in graphene asymmetric hyperbolic metamaterials (AHMM, strongly coupled to terahertz radiation. In contrast to the terahertz amplification in resonant nanocavities, AHMM provides a wide-band THz amplification without any reflection in optically thin graphene multilayers.

  6. An overview on the applications of 'Doyle catalysts' in asymmetric ...

    Indian Academy of Sciences (India)

    The chiral dirhodium(II) carboxamidates are a unique class of chiral catalysts useful for asymmetric inter- and intramolecular cyclopropanation, cyclopropenation and C-H insertion reactions with excellent enantioselectivities. The broad applications of these catalysts in organic syntheses are briefly reviewed.

  7. Purcell effect of asymmetric dipole source distributions in nanowire resonators

    DEFF Research Database (Denmark)

    Filonenko, Konstantin; Duggen, Lars; Adam, Jost

    of the asymmetric source distributions in proximity to the metal nanowire in two configurations: a metal cylinder truncated by the PEC plates and finite metal cylinder in free-space. In order to evaluate Purcell factor the mode eigenvalues are precalculated using Comsol Multiphysics radio frequency module. We...

  8. Purcell effect of asymmetric dipole source distributions in nanowire resonators

    DEFF Research Database (Denmark)

    Filonenko, Konstantin; Duggen, Lars; Adam, Jost


    of the asymmetric source distributions in proximity to the metal nanowire in two configurations: a metal cylinder truncated by the PEC plates and finite metal cylinder in free-space. In order to evaluate Purcell factor the mode eigenvalues are precalculated using Comsol Multiphysics radio frequency module. We...

  9. Free asymmetric transverse vibration of polar orthotropic annular ...

    Indian Academy of Sciences (India)

    R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

    Abstract. In the present paper, free asymmetric transverse vibrations of a non- uniform polar orthotropic annular sector plate, with parabolically varying thickness in the radial direction, have been studied on the basis of classical plate theory. The circular edges of the plate are elastically restrained against translation and.

  10. Asymmetric gold-catalyzed lactonizations in water at room temperature** (United States)

    Handa, Sachin; Lippincott, Daniel J.; Slack, Eric D.; Aue, Donald H.


    Asymmetric gold-catalyzed hydrocarboxylations are reported that show broad substrate scope. The hydrophobic effect associated with in situ-formed aqueous nanomicelles leads to good-to-excellent ee’s of product lactones. In-flask product isolation, along with recycling of the catalyst and reaction medium, combine to arrive at an especially environmentally friendly process. PMID:25124085

  11. Ion pumping in nanochannels using an asymmetric electrode array

    NARCIS (Netherlands)

    Sparreboom, Wouter; Cucu, C.F.; Eijkel, Jan C.T.; van den Berg, Albert; Locascio, L.E.; Gaitan, M.; Paegel, B.M.; Ross, D.J.; Vreeland, W.N.


    We demonstrate an ion pump, consisting of a nanochannel with an AC driven asymmetric electrode array. Our system enables us to actively pump ions using a low driving voltage. In all experiments the electrical double layers are overlapping. Via viscous coupling ion pumping is accompanied by liquid

  12. Research on the Design and Modification of Asymmetric Spur Gear

    Directory of Open Access Journals (Sweden)

    Xiaohe Deng


    Full Text Available A design method for the geometric shape and modification of asymmetric spur gear was proposed, in which the geometric shape and modification of the gear can be obtained directly according to the rack-cutter profile. In the geometric design process of the gear, a rack-cutter with different pressure angles and fillet radius in the driving side and coast side was selected, and the generated asymmetric spur gear profiles also had different pressure angles and fillets accordingly. In the modification design of the gear, the pressure angle modification of rack-cutter was conducted firstly and then the corresponding modified involute gear profile was obtained. The geometric model of spur gears was developed using computer-aided design, and the meshing process was analyzed using finite element simulation method. Furthermore, the transmission error and load sharing ratio of unmodified and modified asymmetric spur gears were investigated. Research results showed that the proposed gear design method was feasible and desired spur gear can be obtained through one time rapid machining by the method. Asymmetric spur gear with better transmission characteristic can be obtained via involute modification.

  13. Symmetric/asymmetric bifurcation behaviours of a bogie system

    DEFF Research Database (Denmark)

    Xue-jun, Gao; Ying-hui, Li; Yuan, Yue


    Based on the bifurcation and stability theory of dynamical systems, the symmetric/asymmetric bifurcation behaviours and chaotic motions of a railway bogie system under a complex nonlinear wheel–rail contact relation are investigated in detail by the ‘resultant bifurcation diagram’ method with slo...

  14. Effect of entry bending moment on exit curvature in asymmetrical ...

    African Journals Online (AJOL)


    In practice, rolling of plate and sheet asymmetry arises due to inequality in roll radii, roll velocity and interface friction. These ... used modified slab method to analyze the asymmetrical plate rolling and to predict strip curvature. Knight et al. ...... This relative motion makes the rotation toward the rougher roll. By applying ...

  15. Interactional Dimension of Online Asynchronous Exchange in an Asymmetric Telecollaboration (United States)

    Loizidou, Dora; Mangenot, François


    The telecollaborative project under study involves, on the one hand, Masters students who are studying to become teachers and who design the tasks as well as tutor them, and, on the other hand, French language students. The relationship in this type of telecollaboration has been shown to be both asymmetric and symmetric. The hypothesis this paper…

  16. Market Efficiency and Price Formation When Dealers are Asymmetrically Informed

    NARCIS (Netherlands)

    Calcagno, R.; Lovo, S.M.


    We consider the effect of asymmetric information on the price formation process in a quote-driven market where one market maker receives a private signal on the security fundamental.A model is presented where market makers repeatedly compete in prices: at each stage a bid-ask auction occurs and the

  17. The asymmetric leader election algorithm: number of survivors near ...

    African Journals Online (AJOL)

    The following classical asymmetric leader election algorithm has obtained quite a bit of attention lately. Starting with n players, each one throws a coin, and the k of them which have each thrown a head (with probability q) go on, and the leader will be found amongst them, using the same strategy. Should nobody advance ...

  18. Eigenstate localization in an asymmetric coupled quantum well pair

    DEFF Research Database (Denmark)

    Mialitsin, Aleksej; Schmult, Stefan; Solov'yov, Ilia


    Optical pumping of a type-I/type-II coupled asymmetric quantum well pair induces a spatially separated two dimensional charge carriers plasma in the well’s wide and narrow parts. Treating the two coupled wells as a single system we find that the eigenstate probability distribution localizes...

  19. Proline-catalysed asymmetric ketol cyclizations: The template ...

    Indian Academy of Sciences (India)


    Abstract. A modified template mechanism based on modelling studies of energy minimised complexes is presented for the asymmetric proline-catalysed cyclization of triketones 1, 2 and 3 to the 2S,3S-ketols. 1a, 2a and 3a respectively. The template model involves a three-point contact as favoured in enzyme– substrate ...

  20. Proline-catalysed asymmetric ketol cyclizations: The template ...

    Indian Academy of Sciences (India)

    A modified template mechanism based on modelling studies of energy minimised complexes is presented for the asymmetric proline-catalysed cyclization of triketones 1, 2 and 3 to the 2, 3-ketols 1a, 2a and 3a respectively. The template model involves a three-point contact as favoured in enzyme-substrate interactions.

  1. Symmetrical and asymmetrical growth restriction in preterm-born children

    NARCIS (Netherlands)

    Bocca-Tjeertes, Inger; Bos, Arend; Kerstjens, Jorien; de Winter, Andrea; Reijneveld, Sijmen

    OBJECTIVE: To determine how symmetric (proportionate; SGR) and asymmetric (disproportionate; AGR) growth restriction influence growth and development in preterms from birth to 4 years. METHODS: This community-based cohort study of 810 children comprised 86 SGR, 61 AGR, and 663 non-growth restricted

  2. Measurement of mode splitting in asymmetric Y-junctions

    NARCIS (Netherlands)

    van der Tol, J.J.G.M.; Laarhuis, J.H.; Laarhuis, Jan


    A measurement procedure is presented for the determination of mode splitting (or mode sorting) in asymmetric Y-junctions. This procedure avoids measurement errors introduced by bends, tapers, small damages in the waveguides outside the coupling region, variation in fiber-chip coupling, etc. It is

  3. Asymmetric block copolymers confined in a thin film

    NARCIS (Netherlands)

    Huinink, HP; Brokken-Zijp, JCM; van Dijk, MA; Sevink, GJA


    We have used a dynamic density functional theory (DDFT) for polymeric systems, to simulate the formation of micro phases in a melt of an asymmetric block copolymer, A(n)B(m)(f(A) = 1/3), both in the bulk and in a thin film. In the DDFT model a polymer is represented as a chain of springs and beads.

  4. Baseline-dependent neutrino oscillations in asymmetrically-warped spacetimes

    CERN Document Server

    Hollenberg, S; Pas, H; Weiler, J T


    We study the possibility to explain the LSND anomaly by means of resonant active-sterile neutrino oscillations in an asymmetrically-warped spacetime. In such extra-dimensional scenarios sterile neutrinos take shortcuts through the extra dimension, which results in new types of resonances in the oscillation probability.

  5. Water transport and purification in nanochannels controlled by asymmetric wettability. (United States)

    Chen, Qinwen; Meng, Lingyi; Li, Qikai; Wang, Dong; Guo, Wei; Shuai, Zhigang; Jiang, Lei


    Biomimetic asymmetric nanochannels have recently attracted increasing attention from researchers, especially in the aspect of the asymmetric wettability (a hydrophilic-hydrophobic system), which can be utilized to control the wetting behavior of aqueous media and to offer a means for guiding water motion. By using molecular dynamics simulations, a design for a potentially efficient water filter is presented based on (n, n) single-walled carbon nanotubes, where n = 6, 8, 10 and 12, asymmetrically modified with hydrophilic groups (carboxyl, -COOH) at one tip and hydrophobic groups (trifluoromethyl, -CF(3) ) at the other. The reduced water density on the hydrophobic sides of the functionalized nanotubes are observed in both pure water and aqueous electrolyte solution, except for the functionalized (6, 6) tube, due to the change of dipole orientation of the single-file water wire within it. The functionalized (8, 8) tube can significantly maintain the low water density on the hydrophobic side. Both (6, 6) and (8, 8) tubes have relatively high energy barriers at their tips for ion permeation, which can be obtained by calculating the potential of mean force. Such tip functionalization of a nanotube therefore suggests the great possibilities of water transport and filtration, dominated by asymmetric wettability. The functionalized (8, 8) tube could act as a nanofluidic channel for water purification, not only for ion exclusion but also as a stable water column structure. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The impact of asymmetric flows on pathological speech (United States)

    Erath, Byron D.; Peterson, Sean D.; Plesniak, Michael W.


    In voiced speech the vocal folds form a divergent glottal passage during the closing phases of the phonatory cycle. Due to the adverse pressure gradient, asymmetric flow develops within the glottis causing the glottal jet to separate from one vocal fold wall, and fully-attach to the opposing wall. The asymmetric pressures that arise from this flow configuration directly influence the vocal fold energy exchange process, and are expected to have the greatest influence on vocal fold motion when pathologies that affect the vocal fold musculature are present. A theoretical flow solution that produces the pressure distributions arising from asymmetric glottal flows is implemented into a two-mass model of speech. The impact of flow asymmetries on pathological vocal fold motion is investigated by modifying the tissue parameters of the speech model to represent unilateral paralysis. The influence of asymmetric flow behavior on pathological vocal fold motion is quantified and compared to the commonly-reported simplified case involving symmetric flow behavior.

  7. Switching the Interpenetration of Confined Asymmetric Polymer Brushes

    NARCIS (Netherlands)

    Abbott, Stephen B.; de Vos, Wiebe Matthijs; Mears, Laura L.E.; Skoda, Maximilian W.A.; Dalgliesh, Robert; Edmondson, Steve; Richardson, Robert M.; Prescott, Stuart W.


    The interpenetration of two polymer brushes on approaching flat surfaces has been investigated. When compacting polymer brushes with an asymmetric charge on each surface, one neutral and the other weakly charged, we find that the brush interpenetration becomes a parameter that can be controlled by

  8. Study on Warm Forging Prosess of 45 Steel Asymmetric Gear (United States)

    Qi, Yushi; Du, Zhiming; Sun, Hongsheng; Chen, Lihua; Wang, Changshun


    Asymmetric gear has complex structure, so using plastic forming technology to process the gear has problems of large forming load, short die life, bad tooth filling, and so on. To solve these problems, this paper presents a radial warm extrusion process of asymmetric gear to reduce the forming load and improve the filling in the toothed corner portion. Using the new mold and No. 45 steel to conducting forming experiments under the optimal forming parameters: billet temperature is 800°C, mold temperature is 250°C, the forming speed is 30mm/s, and the friction coefficient is 0.15, we can obtain the complete asymmetric gear with better surface and tooth filling. Asymmetric gears’ microstructure analysis and mechanical testing showed that the small grain evenly distributed in the region near the addendum circle with high strength; the area near the central portion of the gear had a coarse grain size, uneven distribution and low strength. Significant metal flow lines at the corner part of the gear indicated that a large number of late-forming metal flowed into the tooth cavity filling the corner portion.

  9. GaAs-Based Nanowire Devices with Multiple Asymmetric Gates for Electrical Brownian Ratchets


    Tanaka, Takayuki; Nakano, Yuki; Kasai, Seiya


    GaAs-based nanowire devices having multiple asymmetric gates for electrical Brownian ratchets were fabricated and characterized. From three-dimensional potential simulation results and current–voltage characteristics, we confirmed the formation of the asymmetric potential in our device design. Direct current was generated at room temperature by repeatedly switching the potential in a multiple-asymmetric-gate device on and off. Such current was not observed in either a single-asymmetric-gate d...

  10. Asymmetric Aldol Additions: A Guided-Inquiry Laboratory Activity on Catalysis (United States)

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


    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…

  11. Heterogeneous catalytic materials solid state chemistry, surface chemistry and catalytic behaviour

    CERN Document Server

    Busca, Guido


    Heterogeneous Catalytic Materials discusses experimental methods and the latest developments in three areas of research: heterogeneous catalysis; surface chemistry; and the chemistry of catalysts. Catalytic materials are those solids that allow the chemical reaction to occur efficiently and cost-effectively. This book provides you with all necessary information to synthesize, characterize, and relate the properties of a catalyst to its behavior, enabling you to select the appropriate catalyst for the process and reactor system. Oxides (used both as catalysts and as supports for cata

  12. Catalytic cracking models developed for predictive control purposes

    Directory of Open Access Journals (Sweden)

    Dag Ljungqvist


    Full Text Available The paper deals with state-space modeling issues in the context of model-predictive control, with application to catalytic cracking. Emphasis is placed on model establishment, verification and online adjustment. Both the Fluid Catalytic Cracking (FCC and the Residual Catalytic Cracking (RCC units are discussed. Catalytic cracking units involve complex interactive processes which are difficult to operate and control in an economically optimal way. The strong nonlinearities of the FCC process mean that the control calculation should be based on a nonlinear model with the relevant constraints included. However, the model can be simple compared to the complexity of the catalytic cracking plant. Model validity is ensured by a robust online model adjustment strategy. Model-predictive control schemes based on linear convolution models have been successfully applied to the supervisory dynamic control of catalytic cracking units, and the control can be further improved by the SSPC scheme.

  13. Catalytic combustion with incompletely vaporized residual fuel (United States)

    Rosfjord, T. J.


    Catalytic combustion of fuel lean mixtures of incompletely vaporized residual fuel and air was investigated. The 7.6 cm diameter, graded cell reactor was constructed from zirconia spinel substrate and catalyzed with a noble metal catalyst. Streams of luminous particles exited the rector as a result of fuel deposition and carbonization on the substrate. Similar results were obtained with blends of No. 6 and No. 2 oil. Blends of shale residual oil and No. 2 oil resulted in stable operation. In shale oil blends the combustor performance degraded with a reduced degree of fuel vaporization. In tests performed with No. 2 oil a similar effect was observed.

  14. A Numerical Comparison of Symmetric and Asymmetric Supersonic Wind Tunnels (United States)

    Clark, Kylen D.

    Supersonic wind tunnels are a vital aspect to the aerospace industry. Both the design and testing processes of different aerospace components often include and depend upon utilization of supersonic test facilities. Engine inlets, wing shapes, and body aerodynamics, to name a few, are aspects of aircraft that are frequently subjected to supersonic conditions in use, and thus often require supersonic wind tunnel testing. There is a need for reliable and repeatable supersonic test facilities in order to help create these vital components. The option of building and using asymmetric supersonic converging-diverging nozzles may be appealing due in part to lower construction costs. There is a need, however, to investigate the differences, if any, in the flow characteristics and performance of asymmetric type supersonic wind tunnels in comparison to symmetric due to the fact that asymmetric configurations of CD nozzle are not as common. A computational fluid dynamics (CFD) study has been conducted on an existing University of Michigan (UM) asymmetric supersonic wind tunnel geometry in order to study the effects of asymmetry on supersonic wind tunnel performance. Simulations were made on both the existing asymmetrical tunnel geometry and two axisymmetric reflections (of differing aspect ratio) of that original tunnel geometry. The Reynolds Averaged Navier Stokes equations are solved via NASAs OVERFLOW code to model flow through these configurations. In this way, information has been gleaned on the effects of asymmetry on supersonic wind tunnel performance. Shock boundary layer interactions are paid particular attention since the test section integrity is greatly dependent upon these interactions. Boundary layer and overall flow characteristics are studied. The RANS study presented in this document shows that the UM asymmetric wind tunnel/nozzle configuration is not as well suited to producing uniform test section flow as that of a symmetric configuration, specifically one

  15. A study on naphtha catalytic reforming reactor simulation and analysis


    Liang, Ke-min; Guo, Hai-Yan; Pan, Shi-Wei


    A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation uni...

  16. A study on naphtha catalytic reforming reactor simulation and analysis. (United States)

    Liang, Ke-min; Guo, Hai-yan; Pan, Shi-wei


    A naphtha catalytic reforming unit with four reactors in series is analyzed. A physical model is proposed to describe the catalytic reforming radial flow reactor. Kinetics and thermodynamics equations are selected to describe the naphtha catalytic reforming reactions characteristics based on idealizing the complex naphtha mixture by representing the paraffin, naphthene, and aromatic groups by single compounds. The simulation results based above models agree very well with actual operation unit data.

  17. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion. (United States)

    Pozan, Gulin Selda


    The aim of this work was to study combustion of toluene (1000ppm) over MnO(2) modified with different supports. α-Al(2)O(3) and γ-Al(2)O(3) obtained from Boehmite, γ-Al(2)O(3) (commercial), SiO(2), TiO(2) and ZrO(2) were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO(2) was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO(2)/α-Al(2)O(3)(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289°C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Catalytically favorable surface patterns in Pt-Au nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb


    Motivated by recent experimental demonstrations of novel PtAu nanoparticles with highly enhanced catalytic properties, we present a systematic theoretical study that explores principal catalytic indicators as a function of the particle size and composition. We find that Pt electronic states in the vicinity of the Fermi level combined with a modified electron distribution in the nanoparticle due to Pt-to-Au charge transfer are the origin of the outstanding catalytic properties. From our model we deduce the catalytically favorable surface patterns that induce ensemble and ligand effects. © The Royal Society of Chemistry 2013.

  19. Catalytic hydrothermal liquefaction of water hyacinth. (United States)

    Singh, Rawel; Balagurumurthy, Bhavya; Prakash, Aditya; Bhaskar, Thallada


    Thermal and catalytic hydrothermal liquefaction of water hyacinth was performed at temperatures from 250 to 300 °C under various water hyacinth:H2O ratio of 1:3, 1:6 and 1:12. Reactions were also carried out under various residence times (15-60 min) as well as catalytic conditions (KOH and K2CO3). The use of alkaline catalysts significantly increased the bio-oil yield. Maximum bio-oil yield (23 wt%) comprising of bio-oil1 and bio-oil2 as well as conversion (89%) were observed with 1N KOH solution. (1)H NMR and (13)C NMR data showed that both bio-oil1 and bio-oil2 have high aliphatic carbon content. FTIR of bio-residue indicated that the usage of alkaline catalyst resulted in bio-residue samples with lesser oxygen functionality indicating that catalyst has a marked effect on nature of the bio-residue and helps to decompose biomass to a greater extent compared to thermal case. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Aluminosilicate nanoparticles for catalytic hydrocarbon cracking. (United States)

    Liu, Yu; Pinnavaia, Thomas J


    Aluminosilicate nanoparticles containing 9.0-20 nm mesopores were prepared through the use of protozeolitic nanoclusters as the inorganic precursor and starch as a porogen. The calcined, porogen-free composition containing 2 mol % aluminum exhibited the porosity, hydrothermal stability, and acidity needed for the cracking of very large hydrocarbons. In fact, the hydrothermal stability of the nanoparticles to pure steam at 800 degrees C, along with the cumene cracking activity, surpassed the analogous performance properties of ultrastable Y zeolite, the main catalyst component of commercial cracking catalysts. The remarkable hydrothermal stability and catalytic reactivity of the new nanoparticles are attributable to a unique combination of two factors, the presence of protozeolitic nanoclusters in the pore walls and the unprecedented pore wall thickness (7-15 nm). In addition, the excellent catalytic longevity of the nanoparticles is most likely facilitated by the small domain size of the nanoparticles that greatly improves access to the acid sites on the pore walls and minimizes the diffusion length of coke precursors out of the pores.

  1. SNRB catalytic baghouse laboratory pilot testing

    Energy Technology Data Exchange (ETDEWEB)

    Kudlac, G.A.; Farthing, G.A. (Babcock and Wilcox, Alliance, Ohio (United States)) Szymanski, T. (Norton Co., Akron, OH (United States)); Corbett, R. (Dept. of Energy, Pittsburgh, PA (United States))


    The SOx-NOx-Rox Box{trademark} (SNRB) is an advanced air pollution process patented by Babcock and Wilcox (B and W) that provides for significantly reduced sulfur oxides (SO{sub x}), nitrogen oxides (NO{sub x}), and particulate emissions from coal-fired boilers. The process uses a high-temperature catalytic baghouse for integrating SO{sub x} reduction through injecting an alkali sorbent (such as hydrated lime or sodium bicarbonate), NO{sub x} removal through ammonia injection and selective catalytic reduction (SCR), and particulate collection. The advantages of the process include: compact integration of the emission control technologies into a single component; dry sorbent and by-product handling; and improved SCR catalyst life due to lowered SO{sub x} and particulate levels. The SNRB concept has been successfully demonstrated in a 1,500-ACFM pilot baghouse at B and W's Alliance (Ohio) Research Center. This paper describes the SNRB technology presents the SO{sub x}, NO{sub x}, and particulate removal performance results over a range of operating conditions for the laboratory pilot test program.

  2. Asymmetric nonlinear response of the quantized Hall effect (United States)

    Siddiki, A.; Horas, J.; Kupidura, D.; Wegscheider, W.; Ludwig, S.


    An asymmetric breakdown of the integer quantized Hall effect (IQHE) is investigated. This rectification effect is observed as a function of the current value and its direction in conjunction with an asymmetric lateral confinement potential defining the Hall bar. Our electrostatic definition of the Hall bar via Schottky gates allows a systematic control of the steepness of the confinement potential at the edges of the Hall bar. A softer edge (flatter confinement potential) results in more stable Hall plateaus, i.e. a breakdown at a larger current density. For one soft and one hard edge, the breakdown current depends on its direction, resembling rectification. This nonlinear magneto-transport effect confirms the predictions of an emerging screening theory of the IQHE.

  3. Gamma ray constraints on flavor violating asymmetric dark matter

    DEFF Research Database (Denmark)

    Masina, I.; Panci, P.; Sannino, F.


    We show how cosmic gamma rays can be used to constrain models of asymmetric Dark Matter decaying into lepton pairs by violating flavor. First of all we require the models to explain the anomalies in the charged cosmic rays measured by PAMELA, Fermi and H.E.S.S.; performing combined fits we...... determine the allowed values of the Dark Matter mass and lifetime. For these models, we then determine the constraints coming from the measurement of the isotropic gamma-ray background by Fermi for a complete set of lepton flavor violating primary modes and over a range of DM masses from 100 GeV to 10 Te......V. We find that the Fermi constraints rule out the flavor violating asymmetric Dark Matter interpretation of the charged cosmic ray anomalies....

  4. Asymmetric excitation of surface plasmons by dark mode coupling

    KAUST Repository

    Zhang, X.


    Control over surface plasmons (SPs) is essential in a variety of cutting-edge applications, such as highly integrated photonic signal processing systems, deep-subwavelength lasing, high-resolution imaging, and ultrasensitive biomedical detection. Recently, asymmetric excitation of SPs has attracted enormous interest. In free space, the analog of electromagnetically induced transparency (EIT) in metamaterials has been widely investigated to uniquely manipulate the electromagnetic waves. In the near field, we show that the dark mode coupling mechanism of the classical EIT effect enables an exotic and straightforward excitation of SPs in a metasurface system. This leads to not only resonant excitation of asymmetric SPs but also controllable exotic SP focusing by the use of the Huygens-Fresnel principle. Our experimental findings manifest the potential of developing plasmonic metadevices with unique functionalities.

  5. Multidisciplinary approach to an asymmetric traumatic occlusion: a case report. (United States)

    Pinho, T; Coutinho-Alves, C; Neves, M


    The case of a 47-year-old female patient with an asymmetric traumatic occlusion, great alveolar destruction in the mandibular left central incisor, gingival recession with attachment loss and lack o fkeratinized tissue more accentuated in the crossbite teeth is described. This situation was caused by the traumatic position of the teeth, aggravated by a forced asymmetric anterior position of the mandible and aggravated by mandibular movements. After the extraction of the left central mandibular incisor, keratinized tissue reconstruction and alveolar bone regeneration were performed to obtain enough bone to move the adjacent teeth in this direction and allow the correct placement of an implant at the end of orthodontic treatment. The orthodontic treatment achieved general stable occlusal contacts and esthetic results that were finalized with a definitive prosthetic treatment. This interdisciplinary management was important to solve in the present case the seriously compromised function and esthetics that would never be achieved without this combination.

  6. Left-Right Asymmetric Morphogenesis in the Xenopus Digestive System (United States)

    Muller, Jennifer K.; Prather, D.R.; Nascone-Yoder, N. M.


    The morphogenetic mechanisms by which developing organs become left-right asymmetric entities are unknown. To investigate this issue, we compared the roles of the left and right sides of the Xenopus embryo during the development of anatomic asymmetries in the digestive system. Although both sides contribute equivalently to each of the individual digestive organs, during the initial looping of the primitive gut tube, the left side assumes concave topologies where the right side becomes convex. Of interest, the concave surfaces of the gut tube correlate with expression of the LR gene, Pitx2, and ectopic Pitx2 mRNA induces ectopic concavities in a localized manner. A morphometric comparison of the prospective concave and convex surfaces of the gut tube reveals striking disparities in their rate of elongation but no significant differences in cell proliferation. These results provide insight into the nature of symmetry-breaking morphogenetic events during left-right asymmetric organ development. ?? 2003 Wiley-Liss, Inc.

  7. Asymmetric dark matter models and the LHC diphoton excess

    Energy Technology Data Exchange (ETDEWEB)

    Frandsen, Mads T. [CP" 3-Origins & Danish Institute for Advanced Study DIAS,University of Southern Denmark,Campusvej 55, DK-5230 Odense M (Denmark); Shoemaker, Ian M. [Department of Physics, Department of Astronomy & Astrophysics,Center for Particle and Gravitational Astrophysics, The Pennsylvania State University,104 Davey Laboratory, University Park, PA 16802 (United States)


    The existence of dark matter (DM) and the origin of the baryon asymmetry are persistent indications that the SM is incomplete. More recently, the ATLAS and CMS experiments have observed an excess of diphoton events with invariant mass of about 750 GeV. One interpretation of this excess is decays of a new spin-0 particle with a sizable diphoton partial width, e.g. induced by new heavy weakly charged particles. These are also key ingredients in models cogenerating asymmetric DM and baryons via sphaleron interactions and an initial particle asymmetry. We explore what consequences the new scalar may have for models of asymmetric DM that attempt to account for the similarity of the dark and visible matter abundances.

  8. Control of Wind Turbines during Symmetrical and Asymmetrical Grid Faults

    DEFF Research Database (Denmark)

    Göksu, Ömer

    grid code requirements, which are targeting to make the WPPs operate in a closer manner to the conventional power plants. Common to most of the grid codes, WPPs are required to stay connected during short-circuit grid faults, and also inject reactive current in order to support the grid voltage...... regulation. The uninterrupted operation of WPPs is required even when the grid voltage drops down to zero; and the current injection requirement is defined as positive sequence reactive current irrespective of the fault type; symmetrical or asymmetrical. In this project, the response of full-scale converter...... type wind turbines (WTs), in an AC connected WPP, is investigated and control algorithms are designed for minimum disrupted operation and improved grid support, for both symmetrical and asymmetrical grid faults. WTs’ response with conventional control algorithms is studied regarding the impact...

  9. Multiband Printed Asymmetric Dipole Antenna for LTE/WLAN Applications

    Directory of Open Access Journals (Sweden)

    Chia-Mei Peng


    Full Text Available The ability of a single layer strip fed printed asymmetric dipole antenna, which is composed of top-loading, asymmetric coplanar waveguide (ACPW and stepped-feeding structure, to operate at three wide frequency bands (698~960 MHz, 1710~2620 MHz, and 5150~5850 MHz to cover WLAN and LTE operation has been demonstrated. A prototype of the proposed antenna with 57.5 mm in length, 0.4 mm in thickness, and 5 mm in width is fabricated and experimentally investigated. The experimental results indicate that the VSWR 2.5 : 1 bandwidths achieved were 74.3%, 40.8%, and 18.2% at 700 MHz, 2450 MHz, and 5500 MHz, respectively. Experimental results are shown to verify the validity of theoretical work.

  10. Corporate governance ratings as a means to reduce asymmetric information

    DEFF Research Database (Denmark)

    Balling, Morten; Holm, Claus; Poulsen, Thomas

    Can corporate governance ratings reduce problems of asymmetric information between companies and investors? To answer this question, we set out to examine the information basis for providing such ratings by reviewing corporate governance attributes that are required or recommended in laws...... suggest that rating providers by selecting relevant attributes in an intelligent way can improve the screening of companies according to governance quality. In contrast, it seems questionable that weighting, aggregation and classification of corporate governance attributes considerably improve...... governance ratings as a means to reduce asymmetric information in a more general manner. We propose that the rating process may be seen as consisting of two general activities, namely a data reduction phase, and a data weighting, aggregation and classification phase. Findings based on a Danish data set...

  11. Broadband terahertz metamaterial absorber based on sectional asymmetric structures (United States)

    Gong, Cheng; Zhan, Mingzhou; Yang, Jing; Wang, Zhigang; Liu, Haitao; Zhao, Yuejin; Liu, Weiwei


    We suggest and demonstrate the concept and design of sectional asymmetric structures which can manipulate the metamaterial absorber’s working bandwidth with maintaining the other inherent advantages. As an example, a broadband terahertz perfect absorber is designed to confirm its effectiveness. The absorber’s each cell integrates four sectional asymmetric rings, and the entire structure composed of Au and Si3N4 is only 1.9 μm thick. The simulation results show the bandwidth with absorptivity being larger than 90% is extended by about 2.8 times comparing with the conventional square ring absorber. The composable small cell, ultra-thin, and broadband absorption with polarization and incident angle insensitivity will make the absorber suitable for the applications of focal plane array terahertz imaging. PMID:27571941

  12. Meta-$\\mathcal{PT}$ Symmetry in Asymmetric Directional Couplers

    CERN Document Server

    Ma, Chicheng; Litchinitser, Natalia M


    Despite the benefits that directional coupler based parity-time symmetric systems may offer to the field of integrated optics, the realization of such couplers relies on rather strict design constraints on the waveguide parameters. Here, we investigate directional couplers built of asymmetric waveguides that do not fulfill parity-time symmetry. Nevertheless, we demonstrate that for properly designed parameters, at least one mode of such couplers shows a behavior similar to the one observed in parity-symmetric systems. We find an analytical condition relating gain and loss that enables such a behavior. Moreover, if the individual waveguides composing the asymmetric coupler are designed such that the propagation constants of their modes are identical, the behavior of both super-modes supported by the coupler resembles that of the parity-time symmetric systems.

  13. Asymmetric trienamine catalysis: new opportunities in amine catalysis. (United States)

    Kumar, Indresh; Ramaraju, Panduga; Mir, Nisar A


    Amine catalysis, through HOMO-activating enamine and LUMO-activating iminium-ion formation, is receiving increasing attention among other organocatalytic strategies, for the activation of unmodified carbonyl compounds. Particularly, the HOMO-raising activation concept has been applied to the greatest number of asymmetric transformations through enamine, dienamine, and SOMO-activation strategies. Recently, trienamine catalysis, an extension of amine catalysis, has emerged as a powerful tool for synthetic chemists with a novel activation strategy for polyenals/polyenones. In this review article, we discuss the initial developments of trienamine catalysis for highly asymmetric Diels-Alder reactions with different dienophiles and emerging opportunities for other types of cycloadditions and cascade reactions.

  14. Cosmology in time asymmetric extensions of general relativity

    CERN Document Server

    Leon, Genly


    We investigate the cosmological behavior in a universe governed by time asymmetric extensions of general relativity, which is a novel modified gravity based on the addition of new, time-asymmetric, terms on the Hamiltonian framework, in a way that the algebra of constraints and local physics remain unchanged. Nevertheless, at cosmological scales these new terms can have significant effects that can alter the universe evolution, both at early and late times, and the freedom in the choice of the involved modification function makes the scenario able to produce a huge class of cosmological behaviors. For basic ansatzes of modification, we perform a detailed dynamical analysis, extracting the stable late time solutions. Amongst others, we find that the universe can result in dark-energy dominated, accelerating solutions, even in the absence of an explicit cosmological constant, in which the dark energy can be quintessence-like, phantom-like, or behave as an effective cosmological constant. Moreover, it can result...

  15. Asymmetric molecular-orbital tomography by manipulating electron trajectories (United States)

    Wang, Bincheng; Zhang, Qingbin; Zhu, Xiaosong; Lan, Pengfei; Rezvani, Seyed Ali; Lu, Peixiang


    We present a scheme for tomographic imaging of asymmetric molecular orbital based on high-order harmonic generation with a two-color orthogonally polarized multicycle laser field. With the two-dimensional manipulation of the electron trajectories, the electrons can recollide with the target molecule from two noncollinear directions, and then the dipole moment generated from the single direction can be obtained to reconstructed the asymmetric molecular orbital. The recollision is independent from the molecular structure and the angular dependence of the ionization rate in the external field. For this reason, this scheme can avoid the negative effects arising from the modification of the angle-dependent ionization rate induced by Stark shift and be applied to various molecules.

  16. Asymmetric Hardware Distortions in Receive Diversity Systems: Outage Performance Analysis

    KAUST Repository

    Javed, Sidrah


    This paper studies the impact of asymmetric hardware distortion (HWD) on the performance of receive diversity systems using linear and switched combining receivers. The asymmetric attribute of the proposed model motivates the employment of improper Gaussian signaling (IGS) scheme rather than the traditional proper Gaussian signaling (PGS) scheme. The achievable rate performance is analyzed for the ideal and non-ideal hardware scenarios using PGS and IGS transmission schemes for different combining receivers. In addition, the IGS statistical characteristics are optimized to maximize the achievable rate performance. Moreover, the outage probability performance of the receive diversity systems is analyzed yielding closed form expressions for both PGS and IGS based transmission schemes. HWD systems that employ IGS is proven to efficiently combat the self interference caused by the HWD. Furthermore, the obtained analytic expressions are validated through Monte-Carlo simulations. Eventually, non-ideal hardware transceivers degradation and IGS scheme acquired compensation are quantified through suitable numerical results.

  17. New type of asymmetric fission in proton-rich nuclei

    CERN Document Server

    Andreyev, A N; Huyse, M; Van Duppen, P; Antalic, S; Barzakh, A; Bree, N; Cocolios, T E; Comas, V F; Diriken, J; Fedorov, D; Fedosseev, V; Franchoo, S; Heredia, J A; Ivanov, O; Koster, U; Marsh, B A; Nishio, K; Page, R D; Patronis, N; Seliverstov, M; Tsekhanovich, I; Van den Bergh, P; Van De Walle, J; Venhart, M; Vermote, S; Veselsky, M; Wagemans, C; Ichikawa, T; Iwamoto, A; Moller, P; Sierk, A J


    A very exotic process of ${\\beta}$-delayed fission of $^{180}$Tl is studied in detail by using resonant laser ionization with subsequent mass separation at ISOLDE (CERN). In contrast to common expectations, the fission-fragment mass distribution of the post-${\\beta}$-decay daughter nucleus $^{180}$Hg (N/Z=1.25) is asymmetric. This asymmetry is more surprising since a mass-symmetric split of this extremely neutron-deficient nucleus would lead to two $^{90}$Zr fragments, with magic N=50 and semimagic Z=40. This is a new type of asymmetric fission, not caused by large shell effects related to fragment magic proton and neutron numbers, as observed in the actinide region. The newly measured branching ratio for $\\beta$-delayed fission of $^{180}$Tl is 3.6(7)×10$^{-3}$%, approximately 2 orders of magnitude larger than in an earlier study.

  18. Organocatalytic asymmetric arylation of indoles enabled by azo groups (United States)

    Qi, Liang-Wen; Mao, Jian-Hui; Zhang, Jian; Tan, Bin


    Arylation is a fundamental reaction that can be mostly fulfilled by electrophilic aromatic substitution and transition-metal-catalysed aryl functionalization. Although the azo group has been used as a directing group for many transformations via transition-metal-catalysed aryl carbon-hydrogen (C-H) bond activation, there remain significant unmet challenges in organocatalytic arylation. Here, we show that the azo group can effectively act as both a directing and activating group for organocatalytic asymmetric arylation of indoles via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles have been achieved in good yields with excellent enantioselectivities by utilizing chiral phosphoric acid as catalyst. Furthermore, highly enantioenriched pyrroloindoles bearing two contiguous quaternary chiral centres have also been obtained via a cascade enantioselective formal nucleophilic aromatic substitution-cyclization process. This strategy should be useful in other related research fields and will open new avenues for organocatalytic asymmetric aryl functionalization.

  19. Broadband terahertz metamaterial absorber based on sectional asymmetric structures. (United States)

    Gong, Cheng; Zhan, Mingzhou; Yang, Jing; Wang, Zhigang; Liu, Haitao; Zhao, Yuejin; Liu, Weiwei


    We suggest and demonstrate the concept and design of sectional asymmetric structures which can manipulate the metamaterial absorber's working bandwidth with maintaining the other inherent advantages. As an example, a broadband terahertz perfect absorber is designed to confirm its effectiveness. The absorber's each cell integrates four sectional asymmetric rings, and the entire structure composed of Au and Si3N4 is only 1.9 μm thick. The simulation results show the bandwidth with absorptivity being larger than 90% is extended by about 2.8 times comparing with the conventional square ring absorber. The composable small cell, ultra-thin, and broadband absorption with polarization and incident angle insensitivity will make the absorber suitable for the applications of focal plane array terahertz imaging.

  20. A high voltage asymmetric waveform generator for FAIMS. (United States)

    Canterbury, Jesse D; Gladden, James; Buck, Lon; Olund, Roy; MacCoss, Michael J


    High field asymmetric waveform ion mobility spectrometry (FAIMS) has been used increasingly in recent years as an additional method of ion separation and selection before mass spectrometry. The FAIMS electrodes are relatively simple to design and fabricate for laboratories wishing to implement their own FAIMS designs. However, construction of the electronics apparatus needed to produce the required high magnitude asymmetric electric field oscillating at a frequency of several hundred kilohertz is not trivial. Here we present an entirely custom-built electronics setup capable of supplying the required waveforms and voltages. The apparatus is relatively simple and inexpensive to implement. We also present data acquired on this system demonstrating the use of FAIMS as a gas-phase ion filter interface to an ion trap mass spectrometer. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.