WorldWideScience

Sample records for dispersion-driven isomeric equilibria

  1. Xylene isomerization

    KAUST Repository

    Bilaus, Rakan Sulaiman; Pinnau, Ingo

    2016-01-01

    at isomenzation conditions and producing an isomerized product comprising a higher proportion of p-xylene than in the feed mixture, wherein the catalyst comprises an acidic sulfonated catalytic membrane. Xylene isomenzation can also be coupled with a p

  2. Xylene isomerization

    KAUST Repository

    Bilaus, Rakan Sulaiman

    2016-06-23

    A process for producing xylenes, in particular para-xylene that is less energy intensive than conventional processes is provided. In an embodiment the process comprises contacting a feed mixture in an isomenzation zone with a catalyst at isomenzation conditions and producing an isomerized product comprising a higher proportion of p-xylene than in the feed mixture, wherein the catalyst comprises an acidic sulfonated catalytic membrane. Xylene isomenzation can also be coupled with a p-xylene extraction process, where the raffinate (p-xylene deprived stream) from the extraction process is fed to an isomenzation reactor to produce p-xylene. In an embodiment, the process can comprise: a) providing a feed stream comprising a mixture of xylene isomers including p-xylene; b) extracting p-xylene from the feed stream using a separator to separate the feed stream into a p-xylene rich stream and a p-xylene deprived stream; and c) delivering the p-xylene deprived stream to an isomenzation unit, the isomenzation unit including an acidic sulfonated catalytic membrane, and using the isomenzation unit to produce an isomerized product comprising a higher proportion of p-xylene than in the p-xylene deprived stream delivered to the isomenzation unit. In any one or more aspects, the isomenzation unit can be operated at a temperature in the range of less than 350°, for example about 20°C to about 200°C.

  3. Attractive evolutionary equilibria

    NARCIS (Netherlands)

    Joosten, Reinoud A.M.G.; Roorda, Berend

    2011-01-01

    We present attractiveness, a refinement criterion for evolutionary equilibria. Equilibria surviving this criterion are robust to small perturbations of the underlying payoff system or the dynamics at hand. Furthermore, certain attractive equilibria are equivalent to others for certain evolutionary

  4. A necessary condition for dispersal driven growth of populations with discrete patch dynamics.

    Science.gov (United States)

    Guiver, Chris; Packman, David; Townley, Stuart

    2017-07-07

    We revisit the question of when can dispersal-induced coupling between discrete sink populations cause overall population growth? Such a phenomenon is called dispersal driven growth and provides a simple explanation of how dispersal can allow populations to persist across discrete, spatially heterogeneous, environments even when individual patches are adverse or unfavourable. For two classes of mathematical models, one linear and one non-linear, we provide necessary conditions for dispersal driven growth in terms of the non-existence of a common linear Lyapunov function, which we describe. Our approach draws heavily upon the underlying positive dynamical systems structure. Our results apply to both discrete- and continuous-time models. The theory is illustrated with examples and both biological and mathematical conclusions are drawn. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

  5. Attractive evolutionary equilibria

    OpenAIRE

    Roorda, Berend; Joosten, Reinoud

    2011-01-01

    We present attractiveness, a refinement criterion for evolutionary equilibria. Equilibria surviving this criterion are robust to small perturbations of the underlying payoff system or the dynamics at hand. Furthermore, certain attractive equilibria are equivalent to others for certain evolutionary dynamics. For instance, each attractive evolutionarily stable strategy is an attractive evolutionarily stable equilibrium for certain barycentric ray-projection dynamics, and vice versa.

  6. Isomeric Targets and Beams

    International Nuclear Information System (INIS)

    Oganesyan, Yu.Ts.; Karamyan, S.A.

    1994-01-01

    One of the main topics of modern nuclear physics is the investigation of exotic nuclei including hyper-nuclei, trans fermium elements, proton and neutron rich isotopes near drip lines as well as high-spin excited states and states with anomalous deformation. The isomerism of nuclei is closely related with such phenomena as the alignment of single-particle orbitals, the coexistence of various deformations and the manifestation of intruder-levels from neighbouring shells. The investigation of electromagnetic and nuclear interactions of isomers could give important information on their shell structure and its role in the mechanism of nuclear reactions. For such experiments one can either make isomeric targets (sufficiently long-lived) or use the methods of acceleration of isomeric nuclei. Recently, an exotic 16 + four-quasiparticle isomer of 178 Hf m 2 was produced in a micro weight quantity and the first nuclear reactions on it were successfully observed. The talk describes these experiments as well as new ideas for the continuation of the studies and some advantageous ways for the isomeric beams production by the method of direct acceleration or by the secondary beam method. 35 refs., 15 figs., 8 tabs

  7. Some stable hydromagnetic equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, J L; Oberman, C R; Kulsrud, R M; Frieman, E A [Project Matterhorn, Princeton University, Princeton, NJ (United States)

    1958-07-01

    We have been able to find and investigate the properties of equilibria which are hydromagnetically stable. These equilibria can be obtained, for example, by wrapping conductors helically around the stellarator tube. Systems with I = 3 or 4 are indicated to be optimum for stability purposes. In some cases an admixture of I = 2 fields can be advantageous for achieving equilibrium. (author)

  8. Learning efficient correlated equilibria

    KAUST Repository

    Borowski, Holly P.; Marden, Jason R.; Shamma, Jeff S.

    2014-01-01

    The majority of distributed learning literature focuses on convergence to Nash equilibria. Correlated equilibria, on the other hand, can often characterize more efficient collective behavior than even the best Nash equilibrium. However, there are no existing distributed learning algorithms that converge to specific correlated equilibria. In this paper, we provide one such algorithm which guarantees that the agents' collective joint strategy will constitute an efficient correlated equilibrium with high probability. The key to attaining efficient correlated behavior through distributed learning involves incorporating a common random signal into the learning environment.

  9. Learning efficient correlated equilibria

    KAUST Repository

    Borowski, Holly P.

    2014-12-15

    The majority of distributed learning literature focuses on convergence to Nash equilibria. Correlated equilibria, on the other hand, can often characterize more efficient collective behavior than even the best Nash equilibrium. However, there are no existing distributed learning algorithms that converge to specific correlated equilibria. In this paper, we provide one such algorithm which guarantees that the agents\\' collective joint strategy will constitute an efficient correlated equilibrium with high probability. The key to attaining efficient correlated behavior through distributed learning involves incorporating a common random signal into the learning environment.

  10. Institutions, Equilibria and Efficiency

    DEFF Research Database (Denmark)

    Competition and efficiency is at the core of economic theory. This volume collects papers of leading scholars, which extend the conventional general equilibrium model in important ways. Efficiency and price regulation are studied when markets are incomplete and existence of equilibria in such set...... in OLG, learning in OLG and in games, optimal pricing of derivative securities, the impact of heterogeneity...

  11. Toroidal Extrap Equilibria

    International Nuclear Information System (INIS)

    Scheffel, J.

    1982-04-01

    Ideal MHD-equilibria for the toroidal EXTRAP configuration have been computed with an equilibrium code. The free-boundary prob- lem is solved by using the condition that the current density is proportional to r on a flux surface. It is found that the toroidal Z-pinch, initially induced in the central zero-field region of a transverse octupole field, drifts radially outwards producing an inverse -D shaped cross-section. The plasma current of this high- beta equilibrium may be increased if the plasma is pushed back by altering the external confining magnetic field as demonstrated. (Author)

  12. Resurrecting Equilibria Through Cycles

    DEFF Research Database (Denmark)

    Barnett, Richard C.; Bhattacharya, Joydeep; Bunzel, Helle

    equilibria because they asymptotically violate some economic restriction of the model. The literature has always ruled out such paths. This paper studies a pure-exchange monetary overlapping generations economy in which real balances cycle forever between momentary equilibrium points. The novelty is to show...... that segments of the offer curve that have been previously ignored, can in fact be used to produce asymptotically valid cyclical paths. Indeed, a cycle can bestow dynamic validity on momentary equilibrium points that had erstwhile been classified as dynamically invalid....

  13. Institutions, Equilibria and Efficiency

    DEFF Research Database (Denmark)

    Competition and efficiency is at the core of economic theory. This volume collects papers of leading scholars, which extend the conventional general equilibrium model in important ways. Efficiency and price regulation are studied when markets are incomplete and existence of equilibria in such set......Competition and efficiency is at the core of economic theory. This volume collects papers of leading scholars, which extend the conventional general equilibrium model in important ways. Efficiency and price regulation are studied when markets are incomplete and existence of equilibria...... in such settings is proven under very general preference assumptions. The model is extended to include geographical location choice, a commodity space incorporating manufacturing imprecision and preferences for club-membership, schools and firms. Inefficiencies arising from household externalities or group...... membership are evaluated. Core equivalence is shown for bargaining economies. The theory of risk aversion is extended and the relation between risk taking and wealth is experimentally investigated. Other topics include: determinacy in OLG with cash-in-advance constraints, income distribution and democracy...

  14. Adsorption analysis equilibria and kinetics

    CERN Document Server

    Do, Duong D

    1998-01-01

    This book covers topics of equilibria and kinetics of adsorption in porous media. Fundamental equilibria and kinetics are dealt with for homogeneous as well as heterogeneous particles. Five chapters of the book deal with equilibria and eight chapters deal with kinetics. Single component as well as multicomponent systems are discussed. In kinetics analysis, we deal with the various mass transport processes and their interactions inside a porous particle. Conventional approaches as well as the new approach using Maxwell-Stefan equations are presented. Various methods to measure diffusivity, such

  15. Quantum equilibria for macroscopic systems

    International Nuclear Information System (INIS)

    Grib, A; Khrennikov, A; Parfionov, G; Starkov, K

    2006-01-01

    Nash equilibria are found for some quantum games with particles with spin-1/2 for which two spin projections on different directions in space are measured. Examples of macroscopic games with the same equilibria are given. Mixed strategies for participants of these games are calculated using probability amplitudes according to the rules of quantum mechanics in spite of the macroscopic nature of the game and absence of Planck's constant. A possible role of quantum logical lattices for the existence of macroscopic quantum equilibria is discussed. Some examples for spin-1 cases are also considered

  16. Quantum equilibria for macroscopic systems

    Energy Technology Data Exchange (ETDEWEB)

    Grib, A [Department of Theoretical Physics and Astronomy, Russian State Pedagogical University, St. Petersburg (Russian Federation); Khrennikov, A [Centre for Mathematical Modelling in Physics and Cognitive Sciences Vaexjoe University (Sweden); Parfionov, G [Department of Mathematics, St. Petersburg State University of Economics and Finances (Russian Federation); Starkov, K [Department of Mathematics, St. Petersburg State University of Economics and Finances (Russian Federation)

    2006-06-30

    Nash equilibria are found for some quantum games with particles with spin-1/2 for which two spin projections on different directions in space are measured. Examples of macroscopic games with the same equilibria are given. Mixed strategies for participants of these games are calculated using probability amplitudes according to the rules of quantum mechanics in spite of the macroscopic nature of the game and absence of Planck's constant. A possible role of quantum logical lattices for the existence of macroscopic quantum equilibria is discussed. Some examples for spin-1 cases are also considered.

  17. Inverse plasma equilibria

    International Nuclear Information System (INIS)

    Hicks, H.R.; Dory, R.A.; Holmes, J.A.

    1983-01-01

    We illustrate in some detail a 2D inverse-equilibrium solver that was constructed to analyze tokamak configurations and stellarators (the latter in the context of the average method). To ensure that the method is suitable not only to determine equilibria, but also to provide appropriately represented data for existing stability codes, it is important to be able to control the Jacobian, tilde J is identical to delta(R,Z)/delta(rho, theta). The form chosen is tilde J = J 0 (rho)R/sup l/rho where rho is a flux surface label, and l is an integer. The initial implementation is for a fixed conducting-wall boundary, but the technique can be extended to a free-boundary model

  18. Jump conditions in transonic equilibria

    International Nuclear Information System (INIS)

    Guazzotto, L.; Betti, R.; Jardin, S. C.

    2013-01-01

    In the present paper, the numerical calculation of transonic equilibria, first introduced with the FLOW code in Guazzotto et al.[Phys. Plasmas 11, 604 (2004)], is critically reviewed. In particular, the necessity and effect of imposing explicit jump conditions at the transonic discontinuity are investigated. It is found that “standard” (low-β, large aspect ratio) transonic equilibria satisfy the correct jump condition with very good approximation even if the jump condition is not explicitly imposed. On the other hand, it is also found that high-β, low aspect ratio equilibria require the correct jump condition to be explicitly imposed. Various numerical approaches are described to modify FLOW to include the jump condition. It is proved that the new methods converge to the correct solution even in extreme cases of very large β, while they agree with the results obtained with the old implementation of FLOW in lower-β equilibria.

  19. Pierce instability and bifurcating equilibria

    International Nuclear Information System (INIS)

    Godfrey, B.B.

    1981-01-01

    The report investigates the connection between equilibrium bifurcations and occurrence of the Pierce instability. Electrons flowing from one ground plane to a second through an ion background possess a countable infinity of static equilibria, of which only one is uniform and force-free. Degeneracy of the uniform and simplest non-uniform equilibria at a certain ground plan separation marks the onset of the Pierce instability, based on a newly derived dispersion relation appropriate to all the equilibria. For large ground plane separations the uniform equilibrium is unstable and the non-uniform equilibrium is stable, the reverse of their stability properties at small separations. Onset of the Pierce instability at the first bifurcation of equilibria persists in more complicated geometries, providing a general criterion for marginal stability. It seems probable that bifurcation analysis can be a useful tool in the overall study of stable beam generation in diodes and transport in finite cavities

  20. Isomers chart; Table des isomeres

    Energy Technology Data Exchange (ETDEWEB)

    Dupont-Gautier, P; Chantelot, S; Moisson, N [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-07-01

    The nuclear isomers are nuclides offering the same mass number and the same atomic number, but different energy levels. In the following chart the zero energy ground states are omitted and the metastable isomers, i.e. of non-zero energy, known and of measurable lifetime, are listed. The lower limit of this lifetime was set here to 0.1 x 10{sup -6} s. The various isomers were classified in increasing lifetimes. (authors) [French] Les isomeres nucleaires sont des nucleides presentant le meme nombre de masse et le meme numero atomique, mais des niveaux energetiques differents. Dans la table suivante, on a neglige les etats fondamentaux d'energie nulle et on a recense les isomeres metastables, c'est-a-dire d'energie non nulle, connus et de periode mesurable. La limite inferieure de cette periode a ete fixee ici a 0,1 x 10{sup -6} s. Les differents isomeres ont ete classes par periodes croissantes. (auteurs)

  1. Isomers chart; Table des isomeres

    Energy Technology Data Exchange (ETDEWEB)

    Dupont-Gautier, P.; Chantelot, S.; Moisson, N. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1967-07-01

    The nuclear isomers are nuclides offering the same mass number and the same atomic number, but different energy levels. In the following chart the zero energy ground states are omitted and the metastable isomers, i.e. of non-zero energy, known and of measurable lifetime, are listed. The lower limit of this lifetime was set here to 0.1 x 10{sup -6} s. The various isomers were classified in increasing lifetimes. (authors) [French] Les isomeres nucleaires sont des nucleides presentant le meme nombre de masse et le meme numero atomique, mais des niveaux energetiques differents. Dans la table suivante, on a neglige les etats fondamentaux d'energie nulle et on a recense les isomeres metastables, c'est-a-dire d'energie non nulle, connus et de periode mesurable. La limite inferieure de cette periode a ete fixee ici a 0,1 x 10{sup -6} s. Les differents isomeres ont ete classes par periodes croissantes. (auteurs)

  2. Experimental grounds for nuclear shape isomerism

    International Nuclear Information System (INIS)

    Makarenko, V.E.

    1995-11-01

    Experimental data on fission isomeric states of actinide nuclei - half lives, energies, quantum numbers, decay branches and spectroscopic properties - are discussed. Quite a few results find their explanation in the framework of nuclear shape isomerism hypothesis being the in-thing for about thirty years. Others seem to be the hints to the quasiparticle nature of fission isomers. The problem could be solved by direct measurement of nuclear spin for isomeric states. (author). 44 refs, 1 tab

  3. Collisionless current sheet equilibria

    Science.gov (United States)

    Neukirch, T.; Wilson, F.; Allanson, O.

    2018-01-01

    Current sheets are important for the structure and dynamics of many plasma systems. In space and astrophysical plasmas they play a crucial role in activity processes, for example by facilitating the release of magnetic energy via processes such as magnetic reconnection. In this contribution we will focus on collisionless plasma systems. A sensible first step in any investigation of physical processes involving current sheets is to find appropriate equilibrium solutions. The theory of collisionless plasma equilibria is well established, but over the past few years there has been a renewed interest in finding equilibrium distribution functions for collisionless current sheets with particular properties, for example for cases where the current density is parallel to the magnetic field (force-free current sheets). This interest is due to a combination of scientific curiosity and potential applications to space and astrophysical plasmas. In this paper we will give an overview of some of the recent developments, discuss their potential applications and address a number of open questions.

  4. Quantum optimal control of ozone isomerization

    International Nuclear Information System (INIS)

    Artamonov, Maxim; Ho, Tak-San; Rabitz, Herschel

    2004-01-01

    We present a feasibility study of ozone isomerization based on a recent ab initio potential energy surface and a model Hamiltonian constructed by holding the bond lengths constant and using the valence angle as the isomerization coordinate. Optimal control theory is used to find an electric field that drives isomerization with a yield of 95% to the symmetric metastable triangular form of ozone. A frequency filter is applied as an additional spectral constraint limiting the field bandwidth. A post-facto analysis is performed showing a degree of inherent robustness of the isomerization yield to field noise

  5. Learning to Play Efficient Coarse Correlated Equilibria

    KAUST Repository

    Borowski, Holly P.; Marden, Jason R.; Shamma, Jeff S.

    2018-01-01

    The majority of the distributed learning literature focuses on convergence to Nash equilibria. Coarse correlated equilibria, on the other hand, can often characterize more efficient collective behavior than even the best Nash equilibrium. However

  6. Experiments with neutron-rich isomeric beams

    International Nuclear Information System (INIS)

    Rykaczewski, K.; Lewitowicz, M.; Pfuetzner, M.

    1998-01-01

    A review of experimental results obtained on microsecond-isomeric states in neutron-rich nuclei produced in fragmentation reactions and studied with SISSI-Alpha-LISE3 spectrometer system at GANIL Caen is given. The perspectives of experiments based on secondary reactions with isomeric beams are presented

  7. Partial Cooperative Equilibria: Existence and Characterization

    Directory of Open Access Journals (Sweden)

    Amandine Ghintran

    2010-09-01

    Full Text Available We study the solution concepts of partial cooperative Cournot-Nash equilibria and partial cooperative Stackelberg equilibria. The partial cooperative Cournot-Nash equilibrium is axiomatically characterized by using notions of rationality, consistency and converse consistency with regard to reduced games. We also establish sufficient conditions for which partial cooperative Cournot-Nash equilibria and partial cooperative Stackelberg equilibria exist in supermodular games. Finally, we provide an application to strategic network formation where such solution concepts may be useful.

  8. Stackelberg equilibria and horizontal differentiation

    OpenAIRE

    Lambertini, Luca

    1993-01-01

    This paper proposes a taxonomy of the Stackelberg equilibria emerging from a standard game of horizontal differentiation à la Hotelling in which the strategy set of the sellers in the location stage is the real axis. Repeated leadership appears the most advantageous position. Furthermore, this endogenously yields vertical differentiation between products at equilibrium.

  9. Multiple equilibria of divertor plasmas

    International Nuclear Information System (INIS)

    Vu, H.X.; Prinja, A.K.

    1993-01-01

    A one-dimensional, two-fluid transport model with a temperature-dependent neutral recycling coefficient is shown to give rise to multiple equilibria of divertor plasmas (bifurcation). Numerical techniques for obtaining these multiple equilibria and for examining their stability are presented. Although these numerical techniques have been well known to the scientific community, this is the first time they have been applied to divertor plasma modeling to show the existence of multiple equilibria as well as the stability of these solutions. Numerical and approximate analytical solutions of the present one-dimensional transport model both indicate that there exists three steady-state solutions corresponding to (1) a high-temperature, low-density equilibrium, (2) a low-temperature, high-density equilibrium, and (3) an intermediate-temperature equilibrium. While both the low-temperature and the high-temperature equilibria are stable, with respect to small perturbations in the plasma conditions, the intermediate-temperature equilibrium is physically unstable, i.e., any small perturbation about this equilibrium will cause a transition toward either the high-temperature or low-temperature equilibrium

  10. Nash Equilibria in Fisher Market

    Science.gov (United States)

    Adsul, Bharat; Babu, Ch. Sobhan; Garg, Jugal; Mehta, Ruta; Sohoni, Milind

    Much work has been done on the computation of market equilibria. However due to strategic play by buyers, it is not clear whether these are actually observed in the market. Motivated by the observation that a buyer may derive a better payoff by feigning a different utility function and thereby manipulating the Fisher market equilibrium, we formulate the Fisher market game in which buyers strategize by posing different utility functions. We show that existence of a conflict-free allocation is a necessary condition for the Nash equilibria (NE) and also sufficient for the symmetric NE in this game. There are many NE with very different payoffs, and the Fisher equilibrium payoff is captured at a symmetric NE. We provide a complete polyhedral characterization of all the NE for the two-buyer market game. Surprisingly, all the NE of this game turn out to be symmetric and the corresponding payoffs constitute a piecewise linear concave curve. We also study the correlated equilibria of this game and show that third-party mediation does not help to achieve a better payoff than NE payoffs.

  11. Phase equilibria basic principles, applications, experimental techniques

    CERN Document Server

    Reisman, Arnold

    2013-01-01

    Phase Equilibria: Basic Principles, Applications, Experimental Techniques presents an analytical treatment in the study of the theories and principles of phase equilibria. The book is organized to afford a deep and thorough understanding of such subjects as the method of species model systems; condensed phase-vapor phase equilibria and vapor transport reactions; zone refining techniques; and nonstoichiometry. Physicists, physical chemists, engineers, and materials scientists will find the book a good reference material.

  12. Stability of relative equilibria of three vortices

    DEFF Research Database (Denmark)

    Aref, Hassan

    2009-01-01

    Three point vortices on the unbounded plane have relative equilibria wherein the vortices either form an equilateral triangle or are collinear. While the stability analysis of the equilateral triangle configurations is straightforward, that of the collinear relative equilibria is considerably mor...

  13. Strong Nash Equilibria and the Potential Maimizer

    NARCIS (Netherlands)

    van Megen, F.J.C.; Facchini, G.; Borm, P.E.M.; Tijs, S.H.

    1996-01-01

    A class of non cooperative games characterized by a `congestion e ect' is studied, in which there exists a strong Nash equilibrium, and the set of Nash equilibria, the set of strong Nash equilibria and the set of strategy pro les maximizing the potential function coincide.The structure of the class

  14. A new fundamental type of conformational isomerism

    Science.gov (United States)

    Canfield, Peter J.; Blake, Iain M.; Cai, Zheng-Li; Luck, Ian J.; Krausz, Elmars; Kobayashi, Rika; Reimers, Jeffrey R.; Crossley, Maxwell J.

    2018-06-01

    Isomerism is a fundamental chemical concept, reflecting the fact that the arrangement of atoms in a molecular entity has a profound influence on its chemical and physical properties. Here we describe a previously unclassified fundamental form of conformational isomerism through four resolved stereoisomers of a transoid (BF)O(BF)-quinoxalinoporphyrin. These comprise two pairs of enantiomers that manifest structural relationships not describable within existing IUPAC nomenclature and terminology. They undergo thermal diastereomeric interconversion over a barrier of 104 ± 2 kJ mol-1, which we term `akamptisomerization'. Feasible interconversion processes between conceivable synthesis products and reaction intermediates were mapped out by density functional theory calculations, identifying bond-angle inversion (BAI) at a singly bonded atom as the reaction mechanism. We also introduce the necessary BAI stereodescriptors parvo and amplo. Based on an extended polytope formalism of molecular structure and stereoisomerization, BAI-driven akamptisomerization is shown to be the final fundamental type of conformational isomerization.

  15. Easy Synthesis of Two Positional Isomeric Tetrazole Libraries

    NARCIS (Netherlands)

    Wang, Yuanze; Patil, Pravin; Dömling, Alexander

    2016-01-01

    A fast and efficient synthesis of libraries of positional isomeric 1H-tetrazoles and 5H-tetrazoles, for the purpose of testing binding hypothesis of isomeric tetrazoles in fragment-based drug discovery, is described.

  16. Signaling equilibria in sensorimotor interactions.

    Science.gov (United States)

    Leibfried, Felix; Grau-Moya, Jordi; Braun, Daniel A

    2015-08-01

    Although complex forms of communication like human language are often assumed to have evolved out of more simple forms of sensorimotor signaling, less attention has been devoted to investigate the latter. Here, we study communicative sensorimotor behavior of humans in a two-person joint motor task where each player controls one dimension of a planar motion. We designed this joint task as a game where one player (the sender) possesses private information about a hidden target the other player (the receiver) wants to know about, and where the sender's actions are costly signals that influence the receiver's control strategy. We developed a game-theoretic model within the framework of signaling games to investigate whether subjects' behavior could be adequately described by the corresponding equilibrium solutions. The model predicts both separating and pooling equilibria, in which signaling does and does not occur respectively. We observed both kinds of equilibria in subjects and found that, in line with model predictions, the propensity of signaling decreased with increasing signaling costs and decreasing uncertainty on the part of the receiver. Our study demonstrates that signaling games, which have previously been applied to economic decision-making and animal communication, provide a framework for human signaling behavior arising during sensorimotor interactions in continuous and dynamic environments. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Formation, isomerization, and derivatization of keggin tungstoaluminates.

    Science.gov (United States)

    Jennifer J. Cowan; Alan J. Bailey; Robert A. Heintz; Bao T. Do; Kenneth I. Hardcastle; Craig L. Hill; Ira A. Weinstock

    2001-01-01

    Trends in the stability of ¥á and ©¬-Keggin heteropolytungstates of the second-row main-group heteroatoms Al(III), Si(IV), and P(V) are elaborated by data that establish the roles of kinetic and thermodynamic control in the formation and isomerization of Keggin tungstoaluminates. Slow, room-temperature co-...

  18. Isomeric periodic mesoporous organosilicas with controllable properties

    NARCIS (Netherlands)

    Vercaemst, C.; Ide, I.; Friedrich, H.; de Jong, K.P.; Verpoort, F.; van der Voort, P.

    2009-01-01

    The synthesis procedure for isomeric periodic mesoporous organosilicas with E-configured ethenylene bridges was investigated using the homemade pure E-isomer of 1,2-bis(triethoxysilyl)ethene. The pH, aging temperature and the presence of cosolvents played a key role in obtaining well-ordered

  19. Trimethylphosphide isomerization in lanthanum ions presence

    International Nuclear Information System (INIS)

    Zacharias, M.A.; Massabni, A.M.G.

    1984-01-01

    The integration between the trimethilphosphide and the lanthanum ions carry to the formation of solid complexes in a relation of 6:1 where the ligand is the phosphonate what is resultant of the isomerization of trimetylphosphite. By the RMN -1 H and infra-red spectra the products were characterized. (L.M.J.) [pt

  20. Iodine-Catalyzed Isomerization of Dimethyl Muconate

    Energy Technology Data Exchange (ETDEWEB)

    Settle, Amy E [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Berstis, Laura R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Zhang, Shuting [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Rorrer, Nicholas [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Hu, Haiming [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Richards, Ryan [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Beckham, Gregg T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Crowley, Michael F [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Vardon, Derek R [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2018-04-12

    cis,cis-Muconic acid is a platform biobased chemical that can be upgraded to drop-in commodity and novel monomers. Among the possible drop-in products, dimethyl terephthalate can be synthesized via esterification, isomerization, Diels-Alder cycloaddition, and dehydrogenation. The isomerization of cis,cis-dimethyl muconate (ccDMM) to the trans,trans-form (ttDMM) can be catalyzed by iodine; however, studies have yet to address (i) the mechanism and reaction barriers unique to DMM, and (ii) the influence of solvent, potential for catalyst recycle, and recovery of high-purity ttDMM. To address this gap, we apply a joint computational and experimental approach to investigate iodine-catalyzed isomerization of DMM. Density functional theory calculations identified unique regiochemical considerations due to the large number of halogen-diene coordination schemes. Both transition state theory and experiments estimate significant barrier reductions with photodissociated iodine. Solvent selection was critical for rapid kinetics, likely due to solvent complexation with iodine. Under select conditions, ttDMM yields of 95% were achieved in <1 h with methanol, followed by high purity recovery (>98%) with crystallization. Lastly, post-reaction iodine can be recovered and recycled with minimal loss of activity. Overall, these findings provide new insight into the mechanism and conditions necessary for DMM isomerization with iodine to advance the state-of-the-art for biobased chemicals.

  1. Crystal structure of isomeric boron difluoride acetylnaphtholates

    International Nuclear Information System (INIS)

    Bukvetskij, B.V.; Fedorenko, E.V.; Mirochnik, A.G.; Karasev, V.E.

    2006-01-01

    Crystal structures of luminescent isomeric acetylnaphtholates of boron difluoride are investigated. Full X-ray structural analysis is done at 293 K. Coordinated of atoms, bond angles, bond lengths, interatomic distances are determined. Results of comparative evaluations of the isomers are represented [ru

  2. Cat's claw oxindole alkaloid isomerization induced by common extraction methods

    Directory of Open Access Journals (Sweden)

    Samuel Kaiser

    2013-01-01

    Full Text Available Cat's claw oxindole alkaloids are prone to isomerization in aqueous solution. However, studies on their behavior in extraction processes are scarce. This paper addressed the issue by considering five commonly used extraction processes. Unlike dynamic maceration (DM and ultrasound-assisted extraction, substantial isomerization was induced by static maceration, turbo-extraction and reflux extraction. After heating under reflux in DM, the kinetic order of isomerization was established and equations were fitted successfully using a four-parameter Weibull model (R² > 0.999. Different isomerization rates and equilibrium constants were verified, revealing a possible matrix effect on alkaloid isomerization.

  3. Learning to Play Efficient Coarse Correlated Equilibria

    KAUST Repository

    Borowski, Holly P.

    2018-03-10

    The majority of the distributed learning literature focuses on convergence to Nash equilibria. Coarse correlated equilibria, on the other hand, can often characterize more efficient collective behavior than even the best Nash equilibrium. However, there are no existing distributed learning algorithms that converge to specific coarse correlated equilibria. In this paper, we provide one such algorithm, which guarantees that the agents’ collective joint strategy will constitute an efficient coarse correlated equilibrium with high probability. The key to attaining efficient correlated behavior through distributed learning involves incorporating a common random signal into the learning environment.

  4. Computing Nash equilibria through computational intelligence methods

    Science.gov (United States)

    Pavlidis, N. G.; Parsopoulos, K. E.; Vrahatis, M. N.

    2005-03-01

    Nash equilibrium constitutes a central solution concept in game theory. The task of detecting the Nash equilibria of a finite strategic game remains a challenging problem up-to-date. This paper investigates the effectiveness of three computational intelligence techniques, namely, covariance matrix adaptation evolution strategies, particle swarm optimization, as well as, differential evolution, to compute Nash equilibria of finite strategic games, as global minima of a real-valued, nonnegative function. An issue of particular interest is to detect more than one Nash equilibria of a game. The performance of the considered computational intelligence methods on this problem is investigated using multistart and deflection.

  5. Multiple Equilibria in Noisy Rational Expectations Economies

    DEFF Research Database (Denmark)

    Pálvölgyi, Dömötör; Venter, Gyuri

    with a continuous price function. However, we also construct a tractable class of equilibria with discontinuous prices that have very different economic implications, including (i) jumps and crashes, (ii) significant revisions in uninformed belief due to small changes in the market price, (iii) “upward......-sloping” demand curves, (iv) higher prices leading to future returns that are higher in expectation (price drift) and (v) more positively skewed. Discontinuous equilibria can be arbitrarily close to being fully-revealing. Finally, discontinuous equilibria with the same construction also exist in Hellwig (1980)....

  6. Inefficient equilibria in transition economy

    Directory of Open Access Journals (Sweden)

    Sergei Guriev

    1999-01-01

    Full Text Available The paper studies a general equilibrium in an economy where all market participants face a bid-ask spread. The spread may be caused by indirect business taxes, middlemen rent-seeking, delays in payments or liquidity constraints or price uncertainty. Wherever it comes from the spread causes inefficiency of the market equilibrium. We discuss some institutions that can decrease the inefficiency. One is second currency (barter exchange in the inter-firm transactions. It is shown that the general equilibrium in an economy with second currency is effective though is still different from Arrow–Debreu equilibrium. Another solution can be introduction of mutual trade credit. In the economy with trade credit there are multiple equilibria that are more efficient than original bid-ask spread but still not as efficient as Arrow–Debreu one, too. The implications for firms' integration and applicability to Russian economy are discussed.

  7. Is isomerism a risk factor for intestinal volvulus?

    Science.gov (United States)

    Landisch, Rachel M; Loomba, Rohit S; Salazar, Jose H; Buelow, Matthew W; Frommelt, Michele; Anderson, Robert H; Wagner, Amy J

    2018-03-06

    Isomerism, or heterotaxy syndrome, affects many organ systems anatomically and functionally. Intestinal malrotation is common in patients with isomerism. Despite a low reported risk of volvulus, some physicians perform routine screening and prophylactic Ladd procedures on asymptomatic patients with isomerism who are found to have intestinal malrotation. The primary aim of this study was to determine if isomerism is an independent risk factor for volvulus. Kid's Inpatient Database data from 1997 to 2012 was utilized for this study. Characteristics of admissions with and without isomerism were compared with a particular focus on intestinal malrotation, volvulus, and Ladd procedure. A logistic regression was conducted to determine independent risk factors for volvulus with respect to isomerism. 15,962,403 inpatient admissions were included in the analysis, of which 7970 (0.05%) patients had isomerism, and 6 patients (0.1%) developed volvulus. Isomerism was associated with a 52-fold increase in the odds of intestinal malrotation by univariate analysis. Of 251 with isomerism and intestinal malrotation, only 2.4% experienced volvulus. Logistic regression demonstrated that isomerism was not an independent risk factor for volvulus. Isomerism is associated with an increased risk of intestinal malrotation but is not an independent risk factor for volvulus. Prognosis study. Level III. Copyright © 2018 Elsevier Inc. All rights reserved.

  8. Neoclassical MHD equilibria with ohmic current

    International Nuclear Information System (INIS)

    Tokuda, Shinji; Takeda, Tatsuoki; Okamoto, Masao.

    1989-01-01

    MHD equilibria of tokamak plasmas with neoclassical current effects (neoclassical conductivity and bootstrap current) were calculated self-consistently. Neoclassical effects on JFT-2M tokamak plasmas, sustained by ohmic currents, were studied. Bootstrap currents flow little for L-mode type equilibria because of low attainable values of poloidal beta, β J . H-mode type equilibria give bootstrap currents of 30% ohmic currents for β J attained by JFT-2M and 100% for β J ≥ 1.5, both of which are sufficient to change the current profiles and the resultant MHD equilibria. Neoclassical conductivity which has roughly half value of the classical Spitzer conductivity brings peaked ohmic current profiles to yield low safety factor at the magnetic axis. Neoclassical conductivity reduces the value of effective Z(Z eff ) which is necessary to give the observed one-turn voltage but it needs impurities accumulating at the center when such peaked current profiles are not observed. (author)

  9. Multiple equilibria in a simple elastocapillary system

    KAUST Repository

    Taroni, Michele; Vella, Dominic

    2012-01-01

    properties two stable equilibria may exist, and show via numerical solutions of the dynamic model that it is the initial state of the system that determines which stable equilibrium is ultimately reached. © 2012 Cambridge University Press.

  10. Characterizing gamma fields using isomeric activation ratios

    Science.gov (United States)

    Venkataraman, Ramkumar; Fleming, Ronald F.

    1994-12-01

    Isomeric activities were induced in indium by gamma irradiation in three different gamma fields, through the reactions 115In(γ, γ') 115mIn and 113In(γ, γ') 113mIn. The irradiation fields were (i) the 15 kCi 60Co source available in the University, (ii) the spent fuel gamma irradiator in the pool of the University's Ford Nuclear Reactor (FNR) and (iii) south face of the core of the FNR during routine shut downs. Isomeric activation ratios can serve to characterize gamma fields, provided the response functions of the two (γ, γ') reactions sample different energy regimes of the gamma spectrum present in the irradiation fields. The response of an isomeric activation detector, in turn, depends on the number of activation energy levels of the nuclide and the probabilities with which the activation levels de-populate to the isomeric level. The reaction rate ratio RIn115m/ RIn113m was measured in the three gamma fields. The measured ratios were (i) 1.210 ± 0.011 in the 60Co source, (ii) 1.314 ± 0.060 in the spent fuel gamma irradiator and (iii) 1.298 ± 0.039 in a location alongside the FNR core during routine shut downs. The measured reaction rate ratios are not only close to each other, but close to unity as well. This indicates that the excitation functions for the reactions 115In(γ, γ') 115mIn and 113In(γ, γ') 113mIn have similar shapes and that for the nuclides 115In and 113In, the number of activation energy levels and the probabilities with which they populate the isomeric levels are very similar to each other. Thus, the ratio RIn115m/ RIn113m will not yield any information regarding the shape of gamma spectrum in the field of measurement. However by choosing (γ, γ') reactions with different shapes for the excitation functions one can measure a set of isomeric activation ratios that characterize a given gamma field.

  11. Axisymmetric ideal magnetohydrodynamic equilibria with incompressible flows

    International Nuclear Information System (INIS)

    Tasso, H.; Throumoulopoulos, G.N.

    1997-12-01

    It is shown that the ideal MHD equilibrium states of an axisymmetric plasma with incompressible flows are governed by an elliptic partial differential equation for the poloidal magnetic flux function ψ containing five surface quantities along with a relation for the pressure. Exact equilibria are constructed including those with non vanishing poloidal and toroidal flows and differentially varying radial electric fields. Unlike the case in cylindrical incompressible equilibria with isothermal magnetic surfaces which should have necessarily circular cross sections [G. N. Throumoulopoulos and H. Tasso, Phys. Plasmas 4, 1492 (1997)], no restriction appears on the shapes of the magnetic surfaces in the corresponding axisymmetric equilibria. The latter equilibria satisfy a set of six ordinary differential equations which for flows parallel to the magnetic field B can be solved semianalytically. In addition, it is proved the non existence of incompressible axisymmetric equilibria with (a) purely poloidal flows and (b) non-parallel flows with isothermal magnetic surfaces and vertical stroke B vertical stroke = vertical stroke B vertical stroke (ψ) (omnigenous equilibria). (orig.)

  12. Isomerization of C[sub 4] alkenes

    Science.gov (United States)

    Smith, L.A. Jr.

    1984-11-13

    A method is described for isomerizing isobutene or n-butene to produce a mixture of isobutene and normal butene, and polymerizing at least a portion thereof to produce isobutene/n-butene co-dimer, which comprises feeding at least 80 weight % of either the isobutene or n-butene to a catalytic distillation reactor containing a fixed bed acidic cation exchange resin catalyst packing which provides both the catalyst sites and distillation sites for the reaction products, isomerizing a portion of the isobutene or n-butene to produce a mixture of isobutene and n-butene and reacting at least a portion of the isobutene and n-butene to form co-dimer of isobutene and n-butene, whereby an overhead fraction containing any unreacted isobutene and n-butene and a bottoms fraction containing co-dimer is produced. The result of the reaction is substantially the same regardless whether the feed is isobutene or n-butene. Other aspects of the invention, include combinations of procedures to produce high purity isobutene and n-butene. Either isobutene or n-butene product (depending on the desired product) can be recycled as feed, thus substantially carrying out the isomerization to extinction and total conversion to the desired product. 1 fig.

  13. Thermal E/ Z Isomerization in First Generation Molecular Motors.

    Science.gov (United States)

    Kuwahara, Shunsuke; Suzuki, Yuri; Sugita, Naoya; Ikeda, Mari; Nagatsugi, Fumi; Harada, Nobuyuki; Habata, Yoichi

    2018-04-20

    Determination of a thermal E/ Z isomerization barrier of first generation molecular motors is reported. Stable ( E)-1a directly converts to stable ( Z)-1c without photochemical E/ Z isomerization. The activation Gibbs energy of the isomerization was determined to be 123 kJ mol -1 by circular dichroism spectral changes. Density functional theory calculations show that ( Z)-1c is ∼11.4 kJ mol -1 more stable than ( E)-1a.

  14. On Equilibria of the Two-fluid Model in Magnetohydrodynamics

    International Nuclear Information System (INIS)

    Frantzeskakis, Dimitri J.; Stratis, Ioannis G.; Yannacopoulos, Athanasios N.

    2004-01-01

    We show how the equilibria of the two-fluid model in magnetohydrodynamics can be described by the double curl equation and through the study of this equation we study some properties of these equilibria

  15. Free-boundary perturbed MHD equilibria

    International Nuclear Information System (INIS)

    Nührenberg, C

    2012-01-01

    The concept of perturbed ideal MHD equilibria [Boozer A H and Nuhrenberg C 2006 Phys. Plasmas 13 102501] is employed to study the influence of external error-fields and of small plasma-pressure changes on toroidal plasma equilibria. In tokamak and stellarator free-boundary calculations, benchmarks were successful of the perturbed-equilibrium version of the CAS3D stability code [Nührenberg C et al. 2009 Phys. Rev. Lett. 102 235001] with the ideal MHD equilibrium code NEMEC [Hirshman S P et al. 1986 Comput. Phys. Commun. 43 143].

  16. Two-fluid equilibria with flow

    International Nuclear Information System (INIS)

    Steinhauer, L.

    1999-01-01

    The formalism is developed for flowing two-fluid equilibria. The equilibrium system is governed by a pair of second order partial differential equations for the magnetic stream function and the ion stream function plus a Bernoulli-like equation for the density. There are six arbitrary surface function. There are separate characteristic surfaces for each species, which are the guiding-center surfaces. This system is a generalization of the familiar Grad-Shafranov system for a single-fluid equilibrium without flow, which has only one equation and two arbitrary surface functions. In the case of minimum energy equilibria, the six surface functions take on particular forms. (author)

  17. Existence of pareto equilibria for multiobjective games without compactness

    OpenAIRE

    Shiraishi, Yuya; Kuroiwa, Daishi

    2013-01-01

    In this paper, we investigate the existence of Pareto and weak Pareto equilibria for multiobjective games without compactness. By employing an existence theorem of Pareto equilibria due to Yu and Yuan([10]), several existence theorems of Pareto and weak Pareto equilibria for the multiobjective games are established in a similar way to Flores-B´azan.

  18. Designing bifunctional alkene isomerization catalysts using predictive modelling

    NARCIS (Netherlands)

    Landman, I.R.; Paulson, E.R.; Rheingold, A.L.; Grotjahn, D.B.; Rothenberg, G.

    2017-01-01

    Controlling the isomerization of alkenes is important for the manufacturing of fuel additives, fine-chemicals and pharmaceuticals. But even if isomerization seems to be a simple unimolecular process, the factors that govern catalyst performance are far from clear. Here we present a set of models

  19. Phase equilibria of carbohydrates in polar solvents

    DEFF Research Database (Denmark)

    Jonsdottir, Svava Osk; Rasmussen, Peter

    1999-01-01

    A method for calculating interaction energies and interaction parameters with molecular mechanics methods is extended to predict solid-liquid equilibria (SLE) for saccharides in aqueous solution, giving results in excellent agreement with experimental values. Previously, the method has been shown...

  20. MHD stability of vertically asymmetric tokamak equilibria

    International Nuclear Information System (INIS)

    Dalhed, H.E.; Grimm, R.C.; Johnson, J.L.

    1981-03-01

    The ideal MHD stability properties of a special class of vertically asymmetric tokamak equilibria are examined. The calculations confirm that no major new physical effects are introduced and the modifications can be understood by conventional arguments. The results indicate that significant departures from up-down symmetry can be tolerated before the reduction in β becomes important for reactor operation

  1. Nash equilibria via duality and homological selection

    Indian Academy of Sciences (India)

    1Quantitative Methods and Information Systems Area, Indian Institute ... The original proof of existence of Nash equilibria [13] uses fairly ...... The fiber over a regular point a of the disk Di consists of three inverse images (labeled. A1,A2,A3 in ...

  2. Equilibrator: Modeling Chemical Equilibria with Excel

    Science.gov (United States)

    Vander Griend, Douglas A.

    2011-01-01

    Equilibrator is a Microsoft Excel program for learning about chemical equilibria through modeling, similar in function to EQS4WIN, which is no longer supported and does not work well with newer Windows operating systems. Similar to EQS4WIN, Equilibrator allows the user to define a system with temperature, initial moles, and then either total…

  3. Computation of tokamak equilibria with steady flow

    International Nuclear Information System (INIS)

    Kerner, W.; Tokuda, Shinji

    1987-08-01

    The equations for ideal MHD equilibria with stationary flow are reexamined and addressed as numerically applied to tokamak configurations with a free plasma boundary. Both the isothermal (purely toroidal flow) and the poloidal flow cases are treated. Experiment-relevant states with steady flow (so far only in the toroidal direction) are computed by the modified SELENE40 code. (author)

  4. On the stability of dissipative MHD equilibria

    International Nuclear Information System (INIS)

    Teichmann, J.

    1979-04-01

    The global stability of stationary equilibria of dissipative MHD is studied uisng the direct Liapunov method. Sufficient and necessary conditions for stability of the linearized Euler-Lagrangian system with the full dissipative operators are given. The case of the two-fluid isentropic flow is discussed. (orig.)

  5. Intermediates and Generic Convergence to Equilibria

    DEFF Research Database (Denmark)

    Marcondes de Freitas, Michael; Wiuf, Carsten; Feliu, Elisenda

    2017-01-01

    Known graphical conditions for the generic and global convergence to equilibria of the dynamical system arising from a reaction network are shown to be invariant under the so-called successive removal of intermediates, a systematic procedure to simplify the network, making the graphical conditions...

  6. On the stochastic stability of MHD equilibria

    International Nuclear Information System (INIS)

    Teichmann, J.

    1979-07-01

    The stochastic stability in the large of stationary equilibria of ideal and dissipative magnetohydrodynamics under the influence of stationary random fluctuations is studied using the direct Liapunov method. Sufficient and necessary conditions for stability of the linearized Euler-Lagrangian systems are given. The destabilizing effect of stochastic fluctuations is demonstrated. (orig.)

  7. Isomeric Detergent Comparison for Membrane Protein Stability

    DEFF Research Database (Denmark)

    Cho, Kyung Ho; Hariharan, Parameswaran; Mortensen, Jonas S.

    2016-01-01

    and utility, particularly for eukaryotic membrane proteins and membrane protein complexes. Thus, a number of new agents have been devised; some have made significant contributions to membrane protein structural studies. However, few detergent design principles are available. In this study, we prepared meta...... and ortho isomers of the previously reported para-substituted xylene-linked maltoside amphiphiles (XMAs), along with alkyl chain-length variation. The isomeric XMAs were assessed with three membrane proteins, and the meta isomer with a C12 alkyl chain was most effective at maintaining solubility....../stability of the membrane proteins. We propose that interplay between the hydrophile–lipophile balance (HLB) and alkyl chain length is of central importance for high detergent efficacy. In addition, differences in inter-alkyl-chain distance between the isomers influence the ability of the detergents to stabilise membrane...

  8. Graphene oxide catalyzed cis-trans isomerization of azobenzene

    Directory of Open Access Journals (Sweden)

    Dongha Shin

    2014-09-01

    Full Text Available We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO, where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

  9. Insights in the Rhodium-Catalyzed Tandem Isomerization-Hydroformylation of 10-Undecenitrile: Evidence for a Fast Isomerization Regime

    Directory of Open Access Journals (Sweden)

    Lucas Le Goanvic

    2018-04-01

    Full Text Available The tandem isomerization-hydroformylation of 10-undecenitrile (1 into the corresponding linear aldehyde (2 with a Rh-biphephos system was studied and the formation of internal olefin isomers (1-int-x was monitored over time. The existence of an “isomerization phenomenon” was evidenced, where fast isomerization of 1 into up to 70% of 1-int-x followed by fast back-isomerization of 1-int-x into 1 and, in turn, into 2 occurs. This fast dynamic isomerization regime is favored at high syngas pressure (40 bar and low biphephos-to-Rh ratio (5–10, and it is best observed at relatively high catalyst loadings ([1]0/[Rh] ≤ 3000. The latter regime is indeed evanescent, and gives place to a second stage in which isomerization of internal olefins (and eventual conversion into 2 proceeds much more slowly. The results are tentatively rationalized by the formation of an unstable species that promotes dynamic isomerization and which slowly vanishes or collapses into a Rh-biphephos species which is the one responsible for hydroformylation.

  10. High-pressure fluid-phase equilibria: Experimental methods and systems investigated (2000-2004)

    DEFF Research Database (Denmark)

    Dohrn, Ralf; Peper, Stephanie; Fonseca, José

    2010-01-01

    As a part of a series of reviews, a compilation of systems for which high-pressure phase-equilibrium data were published between 2000 and 2004 is given. Vapor-liquid equilibria, liquid-liquid equilibria, vapor-liquid-liquid equilibria,solid-liquid equilibria, solid-vapor equilibria, solid-vapor-l...

  11. Gyrokinetic magnetohydrodynamics and the associated equilibria

    Science.gov (United States)

    Lee, W. W.; Hudson, S. R.; Ma, C. H.

    2017-12-01

    The gyrokinetic magnetohydrodynamic (MHD) equations, related to the recent paper by W. W. Lee ["Magnetohydrodynamics for collisionless plasmas from the gyrokinetic perspective," Phys. Plasmas 23, 070705 (2016)], and their associated equilibria properties are discussed. This set of equations consists of the time-dependent gyrokinetic vorticity equation, the gyrokinetic parallel Ohm's law, and the gyrokinetic Ampere's law as well as the equations of state, which are expressed in terms of the electrostatic potential, ϕ, and the vector potential, A , and support both spatially varying perpendicular and parallel pressure gradients and the associated currents. The corresponding gyrokinetic MHD equilibria can be reached when ϕ→0 and A becomes constant in time, which, in turn, gives ∇.(J∥+J⊥)=0 and the associated magnetic islands, if they exist. Examples of simple cylindrical geometry are given. These gyrokinetic MHD equations look quite different from the conventional MHD equations, and their comparisons will be an interesting topic in the future.

  12. Multiple equilibria in a simple elastocapillary system

    KAUST Repository

    Taroni, Michele

    2012-09-28

    We consider the elastocapillary interaction of a liquid drop placed between two elastic beams, which are both clamped at one end to a rigid substrate. This is a simple model system relevant to the problem of surface-tension-induced collapse of flexible micro-channels that has been observed in the manufacture of microelectromechanical systems (MEMS). We determine the conditions under which the beams remain separated, touch at a point, or stick along a portion of their length. Surprisingly, we show that in many circumstances multiple equilibrium states are possible. We develop a lubrication-type model for the flow of liquid out of equilibrium and thereby investigate the stability of the multiple equilibria. We demonstrate that for given material properties two stable equilibria may exist, and show via numerical solutions of the dynamic model that it is the initial state of the system that determines which stable equilibrium is ultimately reached. © 2012 Cambridge University Press.

  13. Synthesis and Characterisation of Eight Isomeric Bis(2-pyridyloxynaphthalenes

    Directory of Open Access Journals (Sweden)

    Peter J. Steel

    2006-09-01

    Full Text Available Eight isomeric bis(2-pyridyloxynaphthalenes have been prepared from reactions of 2-bromopyridine with the appropriate dihydroxynaphthalene and the products fully characterised by 1- and 2-D NMR spectroscopy.

  14. Isomerizations of the Nitromethane Radical Cation in the Gas Phase

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Carlsen, Lars; Elbel, Susanne

    1986-01-01

    The concurrent isomerizations of the nitromethane radical cation to its aci-nitromethane and methylnitrite isomers, respectively, has been established based on metastable ion studies and collision activation mass spectrometry. The energy diagram for the ionized nitromethane/aci-nitromethane tauto......The concurrent isomerizations of the nitromethane radical cation to its aci-nitromethane and methylnitrite isomers, respectively, has been established based on metastable ion studies and collision activation mass spectrometry. The energy diagram for the ionized nitromethane...

  15. Uniqueness of Nash equilibria in a quantum Cournot duopoly game

    International Nuclear Information System (INIS)

    Sekiguchi, Yohei; Sakahara, Kiri; Sato, Takashi

    2010-01-01

    A quantum Cournot game whose classical form game has multiple Nash equilibria is examined. Although the classical equilibria fail to be Pareto optimal, the quantum equilibrium exhibits the following two properties: (i) if the measurement of entanglement between strategic variables chosen by the competing firms is sufficiently large, the multiplicity of equilibria vanishes, and (ii) the more strongly the strategic variables are entangled, the more closely the unique equilibrium approaches to the optimal one.

  16. Study of the photochemical isomerization of ergosterol

    International Nuclear Information System (INIS)

    Mermet-Bouvier, Rene

    1972-01-01

    The photochemical reaction scheme of Ergosterol-Vitamin D 2 was studied. The schemes proposed in published literature are described together with earlier methods used for the analysis and determination. The method used is then discussed. In the first part, the factors concerning the changes occurring in molecular systems exposed to radiation, and the formalism used, are examined. Investigations of linear molecular systems and their applications to the reaction scheme of Ergosterol-Vitamin D 2 are discussed. The properties which enable the last three reaction schemes proposed in the literature to be distinguished are described. In the second part, the experimental analytical methods and the determinations made of the different isomers formed are presented. Chromatographic techniques (thin films, columns, gaseous phase) suitable for separating the various isomeric species are used. The existence of 8 isomers was established as well as a transformation occurring in one of them. The ultraviolet and infrared spectra were obtained. A reaction scheme is proposed (in which all the quantum yield values are given) from comparisons between the calculated and experimental values of the eigenvalue of the absolute minimum value λ m and the eigenvector corresponding to V m . (author) [fr

  17. Exogenous empirical-evidence equilibria in perfect-monitoring repeated games yield correlated equilibria

    KAUST Repository

    Dudebout, Nicolas; Shamma, Jeff S.

    2014-01-01

    This paper proves that exogenous empirical-evidence equilibria (xEEEs) in perfect-monitoring repeated games induce correlated equilibria of the associated one-shot game. An empirical-evidence equilibrium (EEE) is a solution concept for stochastic games. At equilibrium, agents' strategies are optimal with respect to models of their opponents. These models satisfy a consistency condition with respect to the actual behavior of the opponents. As such, EEEs replace the full-rationality requirement of Nash equilibria by a consistency-based bounded-rationality one. In this paper, the framework of empirical evidence is summarized, with an emphasis on perfect-monitoring repeated games. A less constraining notion of consistency is introduced. The fact that an xEEE in a perfect-monitoring repeated game induces a correlated equilibrium on the underlying one-shot game is proven. This result and the new notion of consistency are illustrated on the hawk-dove game. Finally, a method to build specific correlated equilibria from xEEEs is derived.

  18. Exogenous empirical-evidence equilibria in perfect-monitoring repeated games yield correlated equilibria

    KAUST Repository

    Dudebout, Nicolas

    2014-12-15

    This paper proves that exogenous empirical-evidence equilibria (xEEEs) in perfect-monitoring repeated games induce correlated equilibria of the associated one-shot game. An empirical-evidence equilibrium (EEE) is a solution concept for stochastic games. At equilibrium, agents\\' strategies are optimal with respect to models of their opponents. These models satisfy a consistency condition with respect to the actual behavior of the opponents. As such, EEEs replace the full-rationality requirement of Nash equilibria by a consistency-based bounded-rationality one. In this paper, the framework of empirical evidence is summarized, with an emphasis on perfect-monitoring repeated games. A less constraining notion of consistency is introduced. The fact that an xEEE in a perfect-monitoring repeated game induces a correlated equilibrium on the underlying one-shot game is proven. This result and the new notion of consistency are illustrated on the hawk-dove game. Finally, a method to build specific correlated equilibria from xEEEs is derived.

  19. Ballooning stable high beta tokamak equilibria

    International Nuclear Information System (INIS)

    Tuda, Takashi; Azumi, Masafumi; Kurita, Gen-ichi; Takizuka, Tomonori; Takeda, Tatsuoki

    1981-04-01

    The second stable regime of ballooning modes is numerically studied by using the two-dimensional tokamak transport code with the ballooning stability code. Using the simple FCT heating scheme, we find that the plasma can locally enter this second stable regime. And we obtained equilibria with fairly high beta (β -- 23%) stable against ballooning modes in a whole plasma region, by taking into account of finite thermal diffusion due to unstable ballooning modes. These results show that a tokamak fusion reactor can operate in a high beta state, which is economically favourable. (author)

  20. Critical beta for analytical spheromak equilibria

    International Nuclear Information System (INIS)

    Freire, E.M.; Clemente, R.A.

    1985-01-01

    The Mercier criterion is applied to two analytical spheromak equilibria, one with a spherical separatrix and the other with a cylindrical one of variable elongation. The maximum beta, defined as the ratio between the plasma pressure and the magnetic pressure averaged over the plasma volume, for which the criterion is satisfied on every magnetic surface, has been obtained. In the spherical model the critical beta is 0.003, while in the cylindrical case it is a function of the elongation of the separatrix with a maximum of 0.083. (author)

  1. Numerical determination of axisymmetric toroidal magnetohydrodynamic equilibria

    International Nuclear Information System (INIS)

    Johnson, J.L.; Dalhed, H.E.; Greene, J.M.

    1978-07-01

    Numerical schemes for the determination of stationary axisymmetric toroidal equilibria appropriate for modeling real experimental devices are given. Iterative schemes are used to solve the elliptic nonlinear partial differential equation for the poloidal flux function psi. The principal emphasis is on solving the free boundary (plasma-vacuum interface) equilibrium problem where external current-carrying toroidal coils support the plasma column, but fixed boundary (e.g., conducting shell) cases are also included. The toroidal current distribution is given by specifying the pressure and either the poloidal current or the safety factor profiles as functions of psi. Examples of the application of the codes to tokamak design at PPPL are given

  2. High temperature phase equilibria and phase diagrams

    CERN Document Server

    Kuo, Chu-Kun; Yan, Dong-Sheng

    2013-01-01

    High temperature phase equilibria studies play an increasingly important role in materials science and engineering. It is especially significant in the research into the properties of the material and the ways in which they can be improved. This is achieved by observing equilibrium and by examining the phase relationships at high temperature. The study of high temperature phase diagrams of nonmetallic systems began in the early 1900s when silica and mineral systems containing silica were focussed upon. Since then technical ceramics emerged and more emphasis has been placed on high temperature

  3. Solid-phase equilibria on Pluto's surface

    Science.gov (United States)

    Tan, Sugata P.; Kargel, Jeffrey S.

    2018-03-01

    Pluto's surface is covered by volatile ices that are in equilibrium with the atmosphere. Multicomponent phase equilibria may be calculated using a thermodynamic equation of state and, without additional assumptions, result in methane-rich and nitrogen-rich solid phases. The former is formed at temperature range between the atmospheric pressure-dependent sublimation and condensation points, while the latter is formed at temperatures lower than the sublimation point. The results, calculated for the observed 11 μbar atmospheric pressure and composition, are consistent with recent work derived from observations by New Horizons.

  4. Guiding Center Equations in Toroidal Equilibria

    International Nuclear Information System (INIS)

    White, Roscoe; Zakharov, Leonid

    2002-01-01

    Guiding center equations for particle motion in a general toroidal magnetic equilibrium configuration are derived using magnetic coordinates. Previous derivations made use of Boozer coordinates, in which the poloidal and toroidal angle variables are chosen so that the Jacobian is inversely proportional to the square of the magnetic field. It is shown that the equations for guiding center motion in any equilibrium possessing nested flux surfaces have exactly the same simple form as those derived in this special case. This allows the use of more spatially uniform coordinates instead of the Boozer coordinates, greatly increasing the accuracy of calculations in large beta and strongly shaped equilibria

  5. A unifying approach to existence of Nash equilibria

    NARCIS (Netherlands)

    Balder, E.J.

    1997-01-01

    An approach initiated in [4] is shown to unify results about the existence of (i) Nash equilibria in games with at most countably many players, (ii) Cournot-Nash equilibrium distributions for large, anonymous games, and (iii) Nash equilibria (both mixed and pure) for continuum games. A new, central

  6. Improving gasoline quality produced from MIDOR light naphtha isomerization unit

    Directory of Open Access Journals (Sweden)

    M.F. Mohamed

    2017-03-01

    Full Text Available Isomerization process became one of the best gasoline production sources, as it gives a high octane product while saving environment from pollution impacts. This paper presents a practical study that aims to improve the gasoline quality and economic income of an existing light naphtha isomerization unit used for octane improvement. The study included selecting the optimum combination of isomerization unit equipment that gives better product specifications for a specified feed. Eight scenarios were studied and simulated to predict the product specs. The original studied unit is MIDOR light naphtha isomerization unit at Alexandria-Egypt that recycles the unconverted hexane (C6. The other studied scenarios were adding fractionators for separating feed iso-pentanes, and recycling unconverted pentanes, hexanes and/or combinations of these fractionators. The results show a change in octane number of gasoline product for a specific feed. Once through process with no extra fractionators has lower octane number of 81 while that with de-iso-pentanizer–de-pentanizer and de-hexanizer produces gasoline with 92.3 octane number. Detailed economic study was done to calculate the return on investment “ROI” for each process option based on equipment, utilities, feed and product prices. Once through simple isomerization unit had the lowest ROI of 14.3% per year while the combination of De-iso-pentanizer with the De-hexanizer had the best ROI of 26.6% per year.

  7. Equilibria of perceptrons for simple contingency problems.

    Science.gov (United States)

    Dawson, Michael R W; Dupuis, Brian

    2012-08-01

    The contingency between cues and outcomes is fundamentally important to theories of causal reasoning and to theories of associative learning. Researchers have computed the equilibria of Rescorla-Wagner models for a variety of contingency problems, and have used these equilibria to identify situations in which the Rescorla-Wagner model is consistent, or inconsistent, with normative models of contingency. Mathematical analyses that directly compare artificial neural networks to contingency theory have not been performed, because of the assumed equivalence between the Rescorla-Wagner learning rule and the delta rule training of artificial neural networks. However, recent results indicate that this equivalence is not as straightforward as typically assumed, suggesting a strong need for mathematical accounts of how networks deal with contingency problems. One such analysis is presented here, where it is proven that the structure of the equilibrium for a simple network trained on a basic contingency problem is quite different from the structure of the equilibrium for a Rescorla-Wagner model faced with the same problem. However, these structural differences lead to functionally equivalent behavior. The implications of this result for the relationships between associative learning, contingency theory, and connectionism are discussed.

  8. Radiochemical study of isomerization of free butyl cations

    International Nuclear Information System (INIS)

    Sinotova, E.N.; Nefedov, V.D.; Skorokhodov, S.S.; Arkhipov, Yu.M.

    1987-01-01

    Ion-molecular reactions of free butyl cations, generated by nuclear chemical method, with carbon monoxide containing small quantities of ethanol vapors are studied. Carbon monoxide was used to fix instable butyl cations in the form of corresponding acyl ions. Ester of α-methyl-butyric acid appears to be the only product of free butyl cation interaction with carbon monoxide in the presence of ethanol vapors. That means, that up to the moment of butyl cation reaction with carbon monoxide, the primary butyl cations are almost completely isomerized into secondary in agreement with results of previous investigations. This allows one to study free butyl cation isomerization process according to ion-molecular reaction product isomeric composition

  9. Isomeric states in 253No and 253Fm

    International Nuclear Information System (INIS)

    Antalic, S.; Kalaninova, Z.; Saro, S.; Venhart, M.; Hessberger, F.P.; Ackermann, D.; Heinz, S.; Kindler, B.; Khuyagbaatar, J.; Kojouharov, I.; Kuusiniemi, P.; Lommel, B.; Mann, R.; Sulignano, B.; Hofmann, S.; Leino, M.; Nishio, K.; Streicher, B.

    2011-01-01

    Nuclear structure and decay of isomeric states in 253 No were investigated. The isotope was produced by the reaction 48 Ca + 207 Pb. The excitation energy of the known single-particle isomeric state (5/2 + [622]) was measured by delayed coincidences between γ-rays and implanted evaporation residues and was placed into the level scheme. In addition, decay of a high-lying multi-quasiparticle isomer in 253 No was studied using e - -γ coincidence measurements. A rotational band populated by its de-excitation was identified in 253 No. A new isomeric state in 253 Fm was observed and a partial-level scheme for this isotope is suggested. In addition γ transitions from excited levels are reported for 253 Md. (orig.)

  10. Isomerization Intermediates In Solution Phase Photochemistry Of Stilbenes

    Science.gov (United States)

    Doany, F. E.; Hochstrasser, R. M.; Greene, B. I.

    1985-04-01

    Picosecond and subpicosecond spectroscopic studies have revealed evidence for an isomerization intermediate between cis and trans in the photoinduced isomerism of both stilbene and biindanyledene ("stiff" stilbene). In stiff stilbene, a transient absorption at 351 nm displays time evolution and viscosity dependence consistent with absorption by a twisted intermediate ("phantom" state) with a lOps lifetime. An analagous bottleneck state with a life-time of 4ps is also consistent with the ground state recovery dynamics of t-stilbene following excitation of c-stilbene when monitored with 0.1ps resolution.

  11. Evaluation of isomeric excitation functions in neutron induced reactions

    International Nuclear Information System (INIS)

    Grudzevich, O.; Ignatyuk, A.; Zolotarev, K.

    1992-01-01

    The possibilities of isomer levels experimental excitation functions description with theoretical models are discussed. It is shown that the experimental data in many cases can be described by theoretical models quite well without parameter fitting. However, large discrepancies are observed for some reactions. In our opinion, these discrepancies are due to uncertainties of discrete level schemes, schemes of gamma-transitions between levels and spin dependence of level density. Small values of isomeric ratios (< 0.1) have been described with the largest errors. The simple formulae for energy dependence of isomeric ratio for (n,g) reaction has been proposed. (author). 53 refs, 10 figs, 8 tabs

  12. cis–trans Isomerization of silybins A and B

    Directory of Open Access Journals (Sweden)

    Michaela Novotná

    2014-05-01

    Full Text Available Methods were developed and optimized for the preparation of the 2,3-cis- and the 10,11-cis-isomers of silybin by the Lewis acid catalyzed (BF3∙OEt2 isomerization of silybins A (1a and B (1b (trans-isomers. The absolute configuration of all optically pure compounds was determined by using NMR and comparing their electronic circular dichroism data with model compounds of known absolute configurations. Mechanisms for cis–trans-isomerization of silybin are proposed and supported by quantum mechanical calculations.

  13. Ternary equilibria in bismuth--indium--lead alloys

    International Nuclear Information System (INIS)

    Liao, K.C.; Johnson, D.L.; Nelson, R.C.

    1975-01-01

    The liquidus surface is characterized by three binary equilibria. One binary extends from the Pb--Bi peritectic to the Pb--In peritectic. The other two extend from In--Bi eutectics, merge at 50 at. percent Bi and 30 at. percent Pb, and end at the Bi--Pb eutectic. Based on analysis of ternary liquidus contours and vertical sections, it is suggested that solidification for high lead and very high indium alloys occurs from two-phase equilibria. Solidification from all other alloys occurs from three-phase equilibria. Four-phase solidification does not occur in this system

  14. On Pure and (approximate) Strong Equilibria of Facility Location Games

    DEFF Research Database (Denmark)

    Hansen, Thomas Dueholm; Telelis, Orestis A.

    2008-01-01

    We study social cost losses in Facility Location games, where n selfish agents install facilities over a network and connect to them, so as to forward their local demand (expressed by a non-negative weight per agent). Agents using the same facility share fairly its installation cost, but every...... agent pays individually a (weighted) connection cost to the chosen location. We study the Price of Stability (PoS) of pure Nash equilibria and the Price of Anarchy of strong equilibria (SPoA), that generalize pure equilibria by being resilient to coalitional deviations. For unweighted agents on metric...

  15. Evaluation of excitation functions for isomeric levels in neutron reactions

    International Nuclear Information System (INIS)

    Grudzevich, O.T.; Zelenetskij, A.V.; Zolotarev, K.I.; Kornilov, N.V.; Pashchenko, A.B.

    1993-07-01

    The authors consider the use of theoretical models to describe experimental excitation functions for isomeric levels in neutron reactions and to predict the cross-sections when no experimental data are available. It is shown that, in many cases, experimental data can be described quite satisfactorily by calculations without adjustment of parameters. For threshold reactions at a neutron energy of ∼ 14 MeV the agreement between calculated and experimental isomeric ratios is ∼ 20%, and is determined mainly by errors in the experimental ratios. However, for some reactions there are considerable differences between experimental and calculated data, which are due, in the authors' opinion, to uncertainties in the schemes of the low-lying levels and of gamma transitions between levels and to the spin dependence of level density. The small isomeric ratio values R<0.1 are described with the lowest accuracy. A formula is suggested for the energy dependence of the isomeric ratio in the (n,γ) reaction. (author)

  16. cis-trans Isomerization of silybins A and B

    Czech Academy of Sciences Publication Activity Database

    Novotná, Michaela; Gažák, Radek; Biedermann, David; Di Meo, F.; Marhol, Petr; Kuzma, Marek; Bednárová, Lucie; Fuksová, Kateřina; Trouillas, P.; Křen, Vladimír

    -, č. 10 (2014), s. 1047-1063 ISSN 1860-5397 R&D Projects: GA ČR GAP207/10/0288; GA MŠk LH13097; GA MŠk(CZ) LD13041 Institutional support: RVO:61388971 ; RVO:61388963 Keywords : isomerization * silibinin * silybin Subject RIV: CC - Organic Chemistry Impact factor: 2.762, year: 2014

  17. Isomerization of β-carotene by titanium tetrachloride catalyst

    Indian Academy of Sciences (India)

    TECS

    2007-05-04

    May 4, 2007 ... antioxidant because of the presence of a long chain of conjugated carbon-carbon double bonds. ... such as extraction, chromatography etc. It has been reported that the chlorinated solvents can promote isomerization of trans conjugated polyenes such as β-carotene during extraction.5. Also, the isomeriza-.

  18. Isomerization of 2-phospha-4-silabicyclo[1.10]butane

    NARCIS (Netherlands)

    Slootweg, J.C.; Ehlers, A.W.; Lammertsma, K.

    2004-01-01

    In analogy with the valence isomerism of the hydrocarbons bicyclobutane, 1,3-butadiene and cyclobutene, the rearrangements for 2-phospha-4-sila- bicyclo[1.1.0]butane were studied at the B3LYP/6-311+G** level of theory. The monocyclic 1,2-dihydro-1,2-phosphasilete is shown to be the thermodynamically

  19. Re-analysis of exponential rigid-rotor astron equilibria

    International Nuclear Information System (INIS)

    Lovelace, R.V.; Larrabee, D.A.; Fleischmann, H.H.

    1978-01-01

    Previous studies of exponential rigid-rotor astron equilibria include particles which are not trapped in the self-field of the configuration. The modification of these studies required to exclude untrapped particles is derived

  20. Surface current equilibria from a geometric point of view

    International Nuclear Information System (INIS)

    Kaiser, R.; Salat, A.

    1993-04-01

    This paper addresses the inverse problem of the existence of surface current MHD equilibria in toroidal geometry with vanishing magnetic field inside. Inverse means that the plasma-vacuum interface rather than the external wall or conductors are given and the latter remain to be determined. This makes a reformulation of the problem possible in geometric terms: What toroidal surfaces with analytic parameterization allow a simple analytic covering by geodesics? If such a covering by geodesics (field lines) exists, their orthogonal trajectories (current lines) also form a simple covering and are described by a function satisfying a nonlinear partial differential equation of the Hamilton-Jacobi type whose coefficients are combinations of the metric elements of the surface. All known equilibria - equilibria with zero and infinite rotational transform and the symmetric ones in the case of finite rotational transform - turn out to be solutions of separable cases of that equation and allow a unified description if the toroidal surface is parametrized in the moving trihedral associated with a closed curve. Analogously to volume current equilibria, the only continuous symmetries compatible with separability are plane, helical and axial symmetry. In the nonseparable case numerical evidence is presented for cases with chaotic behaviour of geodesics, thus restricting possible equilibria for these surfaces. For weak deviation from axisymmetry KAM-type behaviour is observed, i.e. destruction of geodesic coverings with a low rational rotational transform and preservation of those with irrational rotational transform. A previous attempt to establish three-dimensional surface current equilibria on the basis of the KAM theorem is rejected as incomplete, and a complete proof of the existence of equilibria in the weakly nonaxisymmetric case, based on the twist theorem for mappings, is given. Finally, for a certain class of strong deviations from axisymmetry an analytic criterion is

  1. Computation of Stackelberg Equilibria of Finite Sequential Games

    DEFF Research Database (Denmark)

    Bosanski, Branislav; Branzei, Simina; Hansen, Kristoffer Arnsfelt

    2015-01-01

    The Stackelberg equilibrium is a solution concept that describes optimal strategies to commit to: Player~1 (the leader) first commits to a strategy that is publicly announced, then Player~2 (the follower) plays a best response to the leader's choice. We study Stackelberg equilibria in finite...... sequential (i.e., extensive-form) games and provide new exact algorithms, approximate algorithms, and hardness results for finding equilibria for several classes of such two-player games....

  2. Field line diversion properties of finite β-helias equilibria

    International Nuclear Information System (INIS)

    Hayashi, Takaya; Schwenn, Ulrich; Strumberger, Erika.

    1992-01-01

    The diversion properties of the magnetic field outside the last closed magnetic surface of a Helias stellarator configuration are investigated for finite pressure equilibria. The results indicate that a divertor concept which has been developed from the diversion properties of the corresponding vacuum field can be maintained for finite pressure equilibria. Cross-field particle transport is simulated by a simplified scrape-off layer (SOL) model. (author)

  3. On the uniqueness of fully informative rational expectations equilibria

    OpenAIRE

    Peter DeMarzo; Costis Skiadas

    1998-01-01

    This paper analyzes two equivalent equilibrium notions under asymmetric information: risk neutral rational expectations equilibria (rn-REE), and common knowledge equilibria. We show that the set of fully informative rn-REE is a singleton, and we provide necessary and sufficient conditions for the existence of partially informative rn-REE. In a companion paper (DeMarzo and Skiadas (1996)) we show that equilibrium prices for the larger class of quasi-complete economies can be characterized as r...

  4. Determination of 3D Equilibria from Flux Surface Knowledge Only

    International Nuclear Information System (INIS)

    Mynick, H.E.; Pomphrey, N.

    2001-01-01

    We show that the method of Christiansen and Taylor, from which complete tokamak equilibria can be determined given only knowledge of the shape of the flux surfaces, can be extended to 3-dimensional equilibria, such as those of stellarators. As for the tokamak case, the given geometric knowledge has a high degree of redundancy, so that the full equilibrium can be obtained using only a small portion of that information

  5. MINTEQ, Geochemical Equilibria in Ground Water

    International Nuclear Information System (INIS)

    Krupka, K.M.

    1990-01-01

    1 - Description of program or function: MINTEQ is a geochemical program to model aqueous solutions and the interactions of aqueous solutions with hypothesized assemblages of solid phases. It was developed for the Environmental Protection Agency to perform the calculations necessary to simulate the contact of waste solutions with heterogeneous sediments or the interaction of ground water with solidified wastes. MINTEQ can calculate ion speciation/solubility, adsorption, oxidation-reduction, gas phase equilibria, and precipitation/dissolution of solid phases. MINTEQ can accept a finite mass for any solid considered for dissolution and will dissolve the specified solid phase only until its initial mass is exhausted. This ability enables MINTEQ to model flow-through systems. In these systems the masses of solid phases that precipitate at earlier pore volumes can be dissolved at later pore volumes according to thermodynamic constraints imposed by the solution composition and solid phases present. The ability to model these systems permits evaluation of the geochemistry of dissolved traced metals, such as low-level waste in shallow land burial sites. MINTEQ was designed to solve geochemical equilibria for systems composed of one kilogram of water, various amounts of material dissolved in solution, and any solid materials that are present. Systems modeled using MINTEQ can exchange energy and material (open systems) or just energy (closed systems) with the surrounding environment. Each system is composed of a number of phases. Every phase is a region with distinct composition and physically definable boundaries. All of the material in the aqueous solution forms one phase. The gas phase is composed of any gaseous material present, and structurally distinct solid forms a separate phase. 2 - Method of solution: MINTEQ applies the fundamental principles of thermodynamics to solve geochemical equilibria from a set of mass balance equations, one for each component. Because the

  6. Two-dimensional magnetohydrodynamic equilibria with flow and studies of equilibria fluctuations

    International Nuclear Information System (INIS)

    Agim, Y.Z.

    1989-08-01

    A set of reduced ideal MHD equations is derived to investigate equilibria of plasmas with mass flow in general two-dimensional geometry. These equations provide a means of investigating the effects of flow on self-consistent equilibria in a number of new two-dimensional configurations such as helically symmetric configurations with helical axis, which are relevant to stellarators, as well as axisymmetric configurations. It is found that as in the axisymmetric case, general two-dimensional flow equilibria are governed by a second-order quasi-linear partial differential equation for a magnetic flux function, which is coupled to a Bernoulli-type equation for the density. The equation for the magnetic flux function becomes hyperbolic at certain critical flow speeds which follow from its characteristic equation. When the equation is hyperbolic, shock phenomena may exist. As a particular example, unidirectional flow along the lines of symmetry is considered. In this case, the equation mentioned above is always elliptic. An exact solution for the case of helically symmetric unidirectional flow is found and studied to determine flow effects on the magnetic topology. In second part of this thesis, magnetic fluctuations due to the thermally excited MHD waves are investigated using fluid and kinetic models to describe stable, uniform, compressible plasma in the range above the drift wave frequency and below the ion cyclotron frequency. It is shown that the fluid model with resistivity yields spectral densities which are roughly Lorentzian, exhibit equipartition with no apparent cutoff in wavenumber space and a Bohm-type diffusion coefficient. Under certain conditions, the ensuing transport may be comparable to classical values. For a phenomenological cutoff imposed on the spectrum, the typical fluctuating-to-equilibrium magnetic field ratio is found to be of the order of 10 -10

  7. Thermodynamic Equilibria and Extrema Analysis of Attainability Regions and Partial Equilibria

    CERN Document Server

    Gorban, Alexander N; Kaganovich, Boris M; Keiko, Alexandre V; Shamansky, Vitaly A; Shirkalin, Igor A

    2006-01-01

    This book discusses mathematical models that are based on the concepts of classical equilibrium thermodynamics. They are intended for the analysis of possible results of diverse natural and production processes. Unlike the traditional models, these allow one to view the achievable set of partial equilibria with regards to constraints on kinetics, energy and mass exchange and to determine states of the studied systems of interest for the researcher. Application of the suggested models in chemical technology, energy and ecology is illustrated in the examples.

  8. Left cardiac isomerism in the Sonic hedgehog null mouse.

    Science.gov (United States)

    Hildreth, Victoria; Webb, Sandra; Chaudhry, Bill; Peat, Jonathan D; Phillips, Helen M; Brown, Nigel; Anderson, Robert H; Henderson, Deborah J

    2009-06-01

    Sonic hedgehog (Shh) is a secreted morphogen necessary for the production of sidedness in the developing embryo. In this study, we describe the morphology of the atrial chambers and atrioventricular junctions of the Shh null mouse heart. We demonstrate that the essential phenotypic feature is isomerism of the left atrial appendages, in combination with an atrioventricular septal defect and a common atrioventricular junction. These malformations are known to be frequent in humans with left isomerism. To confirm the presence of left isomerism, we show that Pitx2c, a recognized determinant of morphological leftness, is expressed in the Shh null mutants on both the right and left sides of the inflow region, and on both sides of the solitary arterial trunk exiting from the heart. It has been established that derivatives of the second heart field expressing Isl1 are asymmetrically distributed in the developing normal heart. We now show that this population is reduced in the hearts from the Shh null mutants, likely contributing to the defects. To distinguish the consequences of reduced contributions from the second heart field from those of left-right patterning disturbance, we disrupted the movement of second heart field cells into the heart by expressing dominant-negative Rho kinase in the population of cells expressing Isl1. This resulted in absence of the vestibular spine, and presence of atrioventricular septal defects closely resembling those seen in the hearts from the Shh null mutants. The primary atrial septum, however, was well formed, and there was no evidence of isomerism of the atrial appendages, suggesting that these features do not relate to disruption of the contributions made by the second heart field. We demonstrate, therefore, that the Shh null mouse is a model of isomerism of the left atrial appendages, and show that the recognized associated malformations found at the venous pole of the heart in the setting of left isomerism are likely to arise from

  9. The CHEASE code for toroidal MHD equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Luetjens, H. [Ecole Polytechnique, 91 - Palaiseau (France). Centre de Physique Theorique; Bondeson, A. [Chalmers Univ. of Technology, Goeteborg (Sweden). Inst. for Electromagnetic Field Theory and Plasma Physics; Sauter, O. [ITER-San Diego, La Jolla, CA (United States)

    1996-03-01

    CHEASE solves the Grad-Shafranov equation for the MHD equilibrium of a Tokamak-like plasma with pressure and current profiles specified by analytic forms or sets of data points. Equilibria marginally stable to ballooning modes or with a prescribed fraction of bootstrap current can be computed. The code provides a mapping to magnetic flux coordinates, suitable for MHD stability calculations or global wave propagation studies. The code computes equilibrium quantities for the stability codes ERATO, MARS, PEST, NOVA-W and XTOR and for the global wave propagation codes LION and PENN. The two-dimensional MHD equilibrium (Grad-Shafranov) equation is solved in variational form. The discretization uses bicubic Hermite finite elements with continuous first order derivates for the poloidal flux function {Psi}. The nonlinearity of the problem is handled by Picard iteration. The mapping to flux coordinates is carried out with a method which conserves the accuracy of the cubic finite elements. The code uses routines from the CRAY libsci.a program library. However, all these routines are included in the CHEASE package itself. If CHEASE computes equilibrium quantities for MARS with fast Fourier transforms, the NAG library is required. CHEASE is written in standard FORTRAN-77, except for the use of the input facility NAMELIST. CHEASE uses variable names with up to 8 characters, and therefore violates the ANSI standard. CHEASE transfers plot quantities through an external disk file to a plot program named PCHEASE using the UNIRAS or the NCAR plot package. (author) figs., tabs., 34 refs.

  10. Unifying dynamical and structural stability of equilibria

    Science.gov (United States)

    Arnoldi, Jean-François; Haegeman, Bart

    2016-09-01

    We exhibit a fundamental relationship between measures of dynamical and structural stability of linear dynamical systems-e.g. linearized models in the vicinity of equilibria. We show that dynamical stability, quantified via the response to external perturbations (i.e. perturbation of dynamical variables), coincides with the minimal internal perturbation (i.e. perturbations of interactions between variables) able to render the system unstable. First, by reformulating a result of control theory, we explain that harmonic external perturbations reflect the spectral sensitivity of the Jacobian matrix at the equilibrium, with respect to constant changes of its coefficients. However, for this equivalence to hold, imaginary changes of the Jacobian's coefficients have to be allowed. The connection with dynamical stability is thus lost for real dynamical systems. We show that this issue can be avoided, thus recovering the fundamental link between dynamical and structural stability, by considering stochastic noise as external and internal perturbations. More precisely, we demonstrate that a linear system's response to white-noise perturbations directly reflects the intensity of internal white-noise disturbance that it can accommodate before becoming stochastically unstable.

  11. The CHEASE code for toroidal MHD equilibria

    International Nuclear Information System (INIS)

    Luetjens, H.

    1996-03-01

    CHEASE solves the Grad-Shafranov equation for the MHD equilibrium of a Tokamak-like plasma with pressure and current profiles specified by analytic forms or sets of data points. Equilibria marginally stable to ballooning modes or with a prescribed fraction of bootstrap current can be computed. The code provides a mapping to magnetic flux coordinates, suitable for MHD stability calculations or global wave propagation studies. The code computes equilibrium quantities for the stability codes ERATO, MARS, PEST, NOVA-W and XTOR and for the global wave propagation codes LION and PENN. The two-dimensional MHD equilibrium (Grad-Shafranov) equation is solved in variational form. The discretization uses bicubic Hermite finite elements with continuous first order derivates for the poloidal flux function Ψ. The nonlinearity of the problem is handled by Picard iteration. The mapping to flux coordinates is carried out with a method which conserves the accuracy of the cubic finite elements. The code uses routines from the CRAY libsci.a program library. However, all these routines are included in the CHEASE package itself. If CHEASE computes equilibrium quantities for MARS with fast Fourier transforms, the NAG library is required. CHEASE is written in standard FORTRAN-77, except for the use of the input facility NAMELIST. CHEASE uses variable names with up to 8 characters, and therefore violates the ANSI standard. CHEASE transfers plot quantities through an external disk file to a plot program named PCHEASE using the UNIRAS or the NCAR plot package. (author) figs., tabs., 34 refs

  12. Axisymmetric plasma equilibria in a Kerr metric

    Science.gov (United States)

    Elsässer, Klaus

    2001-10-01

    Plasma equilibria near a rotating black hole are considered within the multifluid description. An isothermal two-component plasma with electrons and positrons or ions is determined by four structure functions and the boundary conditions. These structure functions are the Bernoulli function and the toroidal canonical momentum per mass for each species. The quasi-neutrality assumption (no charge density, no toroidal current) allows to solve Maxwell's equations analytically for any axisymmetric stationary metric, and to reduce the fluid equations to one single scalar equation for the stream function \\chi of the positrons or ions, respectively. The basic smallness parameter is the ratio of the skin depth of electrons to the scale length of the metric and fluid quantities, and, in the case of an electron-ion plasma, the mass ratio m_e/m_i. The \\chi-equation can be solved by standard methods, and simple solutions for a Kerr geometry are available; they show characteristic flow patterns, depending on the structure functions and the boundary conditions.

  13. Axisymmetric Plasma Equilibria in General Relativity

    Science.gov (United States)

    Elsässer, Klaus

    Axisymmetric plasma equilibria near a rotating black hole are considered within the multifluid description. An isothermal two-component plasma with electrons and positrons or ions is determined by four structure functions and the boundary conditions. These structure functions are the Bernoulli function and the toroidal canonical momentum per mass for each species; they remain arbitrary if no gain and loss processes are considered, in close analogy to the free flux functions in ideal magnetohydrodynamics. Several simplifying assumptions allow the reduction of the basic equations to one single scalar equation for the stream function χ of positrons or ions, respectively, playing the rôle of the Grad/Shafranov equation in magnetohydrodynamics; in particular, Maxwell's equations can be solved analytically for a quasineutral plasma when both the charge density and the toroidal electric current density are negligible (in contrast to the Tokamak situation). The basic smallness parameter is the ratio of the skin depth of electrons to the scale length of the metric and fluid quantities, and, in the case of an electron-ion plasma, the mass ratio me/mi. The χ-equation can be solved by standard methods, and simple solutions for a Kerr geometry are available; they show characteristic flow patterns, depending on the structure functions and the boundary conditions.

  14. Isotope effects in ion-exchange equilibria in aqueous and mixed solvent systems

    International Nuclear Information System (INIS)

    Gupta, A.R.

    1979-01-01

    Isotope effects in ion-exchange equilibria in aqueous and mixed solvents are analyzed in terms of the general features of ion-exchange equilibria and of isotope effects in chemical equilibria. The special role of solvent fractionation effects in ion-exchange equilibria in mixed solvents is pointed out. The various situations arising in isotope fractionation in ion exchange in mixed solvents due to solvent fractionation effects are theoretically discussed. The experimental data on lithium isotope effects in ion-exchange equilibria in mixed solvents are shown to conform to the above situations. The limitations of ion-exchange equilibria in mixed solvents for isotope fractionation are pointed out. 3 tables

  15. Isomeric rations study for the α + 70 Ge

    International Nuclear Information System (INIS)

    Hora Villano, M.H. da.

    1984-12-01

    Isomeric ratios for 73 Se F,I produced in the reaction α + 70 Ge with incidence laboratory energy ranging from 8 to 28 MeV, have been measured using off-line γ-ray spectroscopy. Relative formation cross-section for isomeric and ground states were obtained with NAT Ge targets. Compound nucleus statistical analyses were performed using computer codes Alice and Julian. Unlike to Alice code, the Julian code predictions agreed quite well with the experimental results. This agreement may be explained by the inclusion of the γ competition in the deexcitation channels of the compound nucleus and by the correct level density calculation of the emission probabilities in the Julian code. Finally angular momentum populations for isomers formations in the reaction 70 Ge(α, n) 73 have been determined. (author)

  16. Determination of the production rate of low intensity isomeric transitions

    International Nuclear Information System (INIS)

    Lakosi, L.; Veres, A.; Tam, N.C.; Pavlicsek, I.

    1992-01-01

    Flat 2π and cylindrical 4π multiwire proportional counters were built for counting for low energy internal conversion electrons from the nuclear isomers 83m Kr, 103m Rh and 189m Os, induced by irradiation with high intensity 60 Co and 4 MeV bremsstrahlung sources. The β-decay of 176m Lu was recorded by a plastic scintillator. In this way higher sensitivities were attained than by detecting γ-rays or characteristic X-rays associated with the isomeric transitions, and the excitation of 189m Os by low energy 137 Cs and 300 kV X-ray sources also became detectable. Comparatively large isomeric activities produced by linac irradiation were standardizing by a Ge spectrometer for calibrating proportional and scintillation counting. (orig.)

  17. Study of the isomeric states of 66As

    International Nuclear Information System (INIS)

    Czajkowski, S.; Blank, B.; Andriamonje, S.; Attallah, F.; Boue, F.; Davi, F.; Del Moral, R.; Fleury, A.; Musquere, A.; Pravikoff, M.S.; Dufour, J-P; Grzywacz, R.; Janas, Z.; Karny, M.; Pfuetzner, M.; Donzaud, C.; Grewe, A.; Heinz, A.; Junghans, A.; Lewitowicz, M.; Sauvestre, J-E.

    1997-01-01

    The most neutron-deficient isotopes in the N = Z region are an important source of information on the neutron-proton interaction far off stability. The isotopes in this region are characterized by an extreme sensitivity of the deformation to the isospin variations. Here the structure of deformed shells are favoring the high spin states the lifetime of which being sufficient long to be observed after flight time of the order of the microsecond. The study of the decay of this isomeric states permits to approach the structure of the first excited levels of this isotopes. Recent experiments at GANIL with the SISSI - LISE 3 spectrometer were performed to study the neutron deficient nucleus 66 As. This nucleus was produced in the fragmentation of 70 MeV/u 78 Kr primary beam in a nickel target. Two new isomeric states have been observed. From the observed γ transitions a decay scheme is proposed

  18. Surface study of mixtures containing cyclic ethers and isomeric chlorobutanes

    International Nuclear Information System (INIS)

    Royo, F.M.; Villares, A.; Martin, S.; Giner, B.; Lafuente, C.

    2007-01-01

    Experimental surface tensions and the corresponding surface tensions deviations for the mixtures containing 1,3-dioxolane or 1,4-dioxane and 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane or 2-chloro-2-methylpropane, measured with a drop volume tensiometer, are reported at the temperatures of 298.15 K and 313.15 K. The excess surface concentrations of isomeric chlorobutanes are also evaluated using a monolayer model

  19. Deconstructing field-induced ketene isomerization through Lagrangian descriptors.

    Science.gov (United States)

    Craven, Galen T; Hernandez, Rigoberto

    2016-02-07

    The time-dependent geometrical separatrices governing state transitions in field-induced ketene isomerization are constructed using the method of Lagrangian descriptors. We obtain the stable and unstable manifolds of time-varying transition states as dynamic phase space objects governing configurational changes when the ketene molecule is subjected to an oscillating electric field. The dynamics of the isomerization reaction are modeled through classical trajectory studies on the Gezelter-Miller potential energy surface and an approximate dipole moment model which is coupled to a time-dependent electric field. We obtain a representation of the reaction geometry, over varying field strengths and oscillation frequencies, by partitioning an initial phase space into basins labeled according to which product state is reached at a given time. The borders between these basins are in agreement with those obtained using Lagrangian descriptors, even in regimes exhibiting chaotic dynamics. Major outcomes of this work are: validation and extension of a transition state theory framework built from Lagrangian descriptors, elaboration of the applicability for this theory to periodically- and aperiodically-driven molecular systems, and prediction of regimes in which isomerization of ketene and its derivatives may be controlled using an external field.

  20. Mathematical Model for Multicomponent Adsorption Equilibria Using Only Pure Component Data

    DEFF Research Database (Denmark)

    Marcussen, Lis

    2000-01-01

    A mathematical model for nonideal adsorption equilibria in multicomponent mixtures is developed. It is applied with good results for pure substances and for prediction of strongly nonideal multicomponent equilibria using only pure component data. The model accounts for adsorbent...

  1. Ballooning mode second stability region for sequences of tokamak equilibria

    International Nuclear Information System (INIS)

    Sugiyama, L.; Mark, J.W.K.

    A numerical study of several sequences of tokamak equilibria derived from two flux conserving sequences confirms the tendency of high n ideal MHD ballooning modes to stabilize for values of the plasma beta greater than a second critical beta, for sufficiently favorable equilibria. The major stabilizing effect of increasing the inverse rotational transform profile q(Psi) for equilibria with the same flux surface geometry is shown. The unstable region shifts toward larger shear d ln q/d ln γ and the width of the region measured in terms of the poloidal beta or a pressure gradient parameter, for fixed shear, decreases. The smaller aspect ratio sequences are more sensitive to changes in q and have less stringent limits on the attainable value of the plasma beta in the high beta stable region. Finally, the disconnected mode approximation is shown to provide a reasonable description of the second high beta stability boundary

  2. Nematic Equilibria on a Two-Dimensional Annulus

    KAUST Repository

    Lewis, A. H.; Aarts, D. G. A. L.; Howell, P. D.; Majumdar, A.

    2017-01-01

    We study planar nematic equilibria on a two-dimensional annulus with strong and weak tangent anchoring, in the Oseen–Frank theoretical framework. We analyze a radially invariant defect-free state and compute analytic stability criteria for this state in terms of the elastic anisotropy, annular aspect ratio, and anchoring strength. In the strong anchoring case, we define and characterize a new spiral-like equilibrium which emerges as the defect-free state loses stability. In the weak anchoring case, we compute stability diagrams that quantify the response of the defect-free state to radial and azimuthal perturbations. We study sector equilibria on sectors of an annulus, including the effects of weak anchoring and elastic anisotropy, giving novel insights into the correlation between preferred numbers of boundary defects and the geometry. We numerically demonstrate that these sector configurations can approximate experimentally observed equilibria with boundary defects.

  3. Numerical computation of FCT equilibria by inverse equilibrium method

    International Nuclear Information System (INIS)

    Tokuda, Shinji; Tsunematsu, Toshihide; Takeda, Tatsuoki

    1986-11-01

    FCT (Flux Conserving Tokamak) equilibria were obtained numerically by the inverse equilibrium method. The high-beta tokamak ordering was used to get the explicit boundary conditions for FCT equilibria. The partial differential equation was reduced to the simultaneous quasi-linear ordinary differential equations by using the moment method. The regularity conditions for solutions at the singular point of the equations can be expressed correctly by this reduction and the problem to be solved becomes a tractable boundary value problem on the quasi-linear ordinary differential equations. This boundary value problem was solved by the method of quasi-linearization, one of the shooting methods. Test calculations show that this method provides high-beta tokamak equilibria with sufficiently high accuracy for MHD stability analysis. (author)

  4. Hydrostatic Equilibria of Rotating Stars with Realistic Equation of State

    Science.gov (United States)

    Yasutake, Nobutoshi; Fujisawa, Kotaro; Okawa, Hirotada; Yamada, Shoichi

    Stars rotate generally, but it is a non-trivial issue to obtain hydrostatic equilibria for rapidly rotating stars theoretically, especially for baroclinic cases, in which the pressure depends not only on the density, but also on the temperature and compositions. It is clear that the stellar structures with realistic equation of state are the baroclinic cases, but there are not so many studies for such equilibria. In this study, we propose two methods to obtain hydrostatic equilibria considering rotation and baroclinicity, namely the weak-solution method and the strong-solution method. The former method is based on the variational principle, which is also applied to the calculation of the inhomogeneous phases, known as the pasta structures, in crust of neutron stars. We found this method might break the balance equation locally, then introduce the strong-solution method. Note that our method is formulated in the mass coordinate, and it is hence appropriated for the stellar evolution calculations.

  5. Nematic Equilibria on a Two-Dimensional Annulus

    KAUST Repository

    Lewis, A. H.

    2017-01-16

    We study planar nematic equilibria on a two-dimensional annulus with strong and weak tangent anchoring, in the Oseen–Frank theoretical framework. We analyze a radially invariant defect-free state and compute analytic stability criteria for this state in terms of the elastic anisotropy, annular aspect ratio, and anchoring strength. In the strong anchoring case, we define and characterize a new spiral-like equilibrium which emerges as the defect-free state loses stability. In the weak anchoring case, we compute stability diagrams that quantify the response of the defect-free state to radial and azimuthal perturbations. We study sector equilibria on sectors of an annulus, including the effects of weak anchoring and elastic anisotropy, giving novel insights into the correlation between preferred numbers of boundary defects and the geometry. We numerically demonstrate that these sector configurations can approximate experimentally observed equilibria with boundary defects.

  6. Numerical calculation of axisymmetric non-neutral plasma equilibria

    International Nuclear Information System (INIS)

    Spencer, R.L.; Rasband, S.N.; Vanfleet, R.R.

    1993-01-01

    Efficient techniques for computing axisymmetric non-neutral plasma equilibria are described. These equilibria may be obtained either by requiring global thermal equilibrium, by specifying the midplane radial density profile, or by specifying the radial profile of ∫n dz. Both splines and finite-differences are used, and the accuracy of the two is compared by using a new characterization of the thermal equilibrium density profile which gives a simple formula for estimating the radial and axial gradient scale lengths of thermal equilibria. It is found that for global thermal equilibrium 1% accuracy is achieved with splines if the distance between neighboring splines is about two Debye lengths while finite differences require a grid spacing of about one-half Debye length to achieve the same accuracy

  7. Ideal MHD beta-limits of poloidally asymmetric equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Todd, A.M.M.; Miller, A.E.; Grimm, R.C.; Okabayashi, M.; Dalhed, H.E. Jr.

    1981-05-01

    The ideal MHD stability of poloidally asymmetric equilibria, which are typical of a tokamak reactor design with a single-null poloidal divertor is examined. As with symmetric equilibria, stability to non-axisymmetric modes improves with increasing triangularity and ellipticity, and with lower edge safety factor. Pressure profiles optimized with respect to ballooning stability are obtained for an asymmetric shape, resulting in ..beta../sub critical/ approx. = 5.7%. The corresponding value for an equivalent symmetric shape is ..beta../sub critical/ approx. = 6.5%.

  8. Ideal MHD beta-limits of poloidally asymmetric equilibria

    International Nuclear Information System (INIS)

    Todd, A.M.M.; Miller, A.E.; Grimm, R.C.; Okabayashi, M.; Dalhed, H.E. Jr.

    1981-05-01

    The ideal MHD stability of poloidally asymmetric equilibria, which are typical of a tokamak reactor design with a single-null poloidal divertor is examined. As with symmetric equilibria, stability to non-axisymmetric modes improves with increasing triangularity and ellipticity, and with lower edge safety factor. Pressure profiles optimized with respect to ballooning stability are obtained for an asymmetric shape, resulting in β/sub critical/ approx. = 5.7%. The corresponding value for an equivalent symmetric shape is β/sub critical/ approx. = 6.5%

  9. Nash Equilibria in Symmetric Graph Games with Partial Observation

    DEFF Research Database (Denmark)

    Bouyer, Patricia; Markey, Nicolas; Vester, Steen

    2017-01-01

    We investigate a model for representing large multiplayer games, which satisfy strong symmetry properties. This model is made of multiple copies of an arena; each player plays in his own arena, and can partially observe what the other players do. Therefore, this game has partial information...... and symmetry constraints, which make the computation of Nash equilibria difficult. We show several undecidability results, and for bounded-memory strategies, we precisely characterize the complexity of computing pure Nash equilibria for qualitative objectives in this game model....

  10. Nash Equilibria in Symmetric Games with Partial Observation

    DEFF Research Database (Denmark)

    Bouyer, Patricia; Markey, Nicolas; Vester, Steen

    2014-01-01

    We investigate a model for representing large multiplayer games, which satisfy strong symmetry properties. This model is made of multiple copies of an arena; each player plays in his own arena, and can partially observe what the other players do. Therefore, this game has partial information...... and symmetry constraints, which make the computation of Nash equilibria difficult. We show several undecidability results, and for bounded-memory strategies, we precisely characterize the complexity of computing pure Nash equilibria (for qualitative objectives) in this game model....

  11. Recent progress in the relative equilibria of point vortices — In memoriam Hassan Aref

    DEFF Research Database (Denmark)

    Beelen, Peter; Brøns, Morten; Krishnamurthy, Vikas S.

    2013-01-01

    Hassan Aref, who sadly passed away in 2011, was one of the world's leading researchers in the dynamics and equilibria of point vortices. We review two problems on the subject of point vortex relative equilibria in which he was engaged at the time of his death: bilinear relative equilibria...

  12. Evaluation of a Mathematical Model for Single Component Adsorption Equilibria with Reference to the Prediction of Multicomponent Adsorption Equilibria

    DEFF Research Database (Denmark)

    Krøll, Annette Elisabeth; Marcussen, Lis

    1997-01-01

    An equilibrium equation for pure component adsorption is compared to experiments and to the vacancy solution theory. The investigated equilibrium equation is a special case of a model for prediction of multicomponent adsorption equilibria.The vacancy solution theory for multicomponent systems...... requires binary experimental data for determining the interaction parameters of the Wilson equation; thus a large number of experiments are needed. The multicomponent equilibria model which is investigated for single component systems in this work is based on pure component data only. This means...... that the requirement for experimental data is reduced significantly.The two adsorption models are compared, using experimental pure gas adsorption data found in literature. The results obtained by the models are in close agreement for pure component equilibria and they give a good description of the experimental data...

  13. Tracer kinetic investigations on isomerization and synthesis of /sup 8/C-aromates. II. Isomerization of ethylbenzene by means of heterogeneous catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dermietzel, J; Roesseler, M; Jockisch, W; Wienhold, C [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung; Franke, H; Klempin, J; Barz, H J [VEB Petrolchemisches Kombinat Schwedt (German Democratic Republic)

    1978-01-01

    The mechanism of ethylbenzene isomerization on Pt/Al/sub 2/O/sub 3/ catalysts by means of /sup 14/C labelled compounds has been investigated, measuring the isotope distribution between ring and alkyl carbon atoms. The results suggest that ethylbenzene isomerizes via structure rearrangement involving ring carbon atoms. A similar mechanism takes place in xylene isomerization under increased hydrogen partial pressure, while under normal pressure 1,2-methyl group shifting is dominating. All three xylenes are formed from ethylbenzene by parallel reactions.

  14. Combined Function of Brønsted and Lewis Acidity in the Zeolite-Catalyzed Isomerization of Glucose to Fructose in Alcohols

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Riisager, Anders; Taarning, Esben

    2016-01-01

    Glucose conversion via fructose to useful chemicals and fuels has attracted considerable attention. Isomerization of glucose to fructose can proceed along several different reaction pathways involving different sugar intermediates and isomeric forms. Presently, the roles of the substrate isomeric...

  15. Pion condensation and density isomerism in nuclear matter

    International Nuclear Information System (INIS)

    Hecking, P.; Weise, W.

    1979-01-01

    The possible existence of density isomers in nuclear matter, induced by pion condensation, is discussed; the nuclear equation of state is treated within the framework of the sigma model. Repulsive short-range baryon-baryon correlations, the admixture of Δ (1232) isobars and finite-range pion-baryon vertex form factors are taken into account. The strong dependence of density isomerism on the high density extrapolation of the equation of state for normal nuclear matter is also investigated. We find that, once finite range pion-baryon vertices are introduced, the appearance of density isomers becomes unlikely

  16. Synthesis of heterocycles through transition-metal-catalyzed isomerization reactions

    DEFF Research Database (Denmark)

    Ishøy, Mette; Nielsen, Thomas Eiland

    2014-01-01

    of structurally complex and diverse heterocycles. In this Concept article, we attempt to cover this area of research through a selection of recent versatile examples. A sea of opportunities! Transition-metal-catalyzed isomerization of N- and O-allylic compounds provides a mild, selective and synthetically...... versatile method to form iminium and oxocarbenium ions. Given the number of reactions involving these highly electrophilic intermediates, this concept provides a sea of opportunities for heterocycle synthesis, (see scheme; Nu=nucleophile). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim....

  17. Geometrical Optimization Approach to Isomerization: Models and Limitations.

    Science.gov (United States)

    Chang, Bo Y; Shin, Seokmin; Engel, Volker; Sola, Ignacio R

    2017-11-02

    We study laser-driven isomerization reactions through an excited electronic state using the recently developed Geometrical Optimization procedure. Our goal is to analyze whether an initial wave packet in the ground state, with optimized amplitudes and phases, can be used to enhance the yield of the reaction at faster rates, driven by a single picosecond pulse or a pair of femtosecond pulses resonant with the electronic transition. We show that the symmetry of the system imposes limitations in the optimization procedure, such that the method rediscovers the pump-dump mechanism.

  18. Isomeric island in the vicinity of 66Fe

    International Nuclear Information System (INIS)

    Daugas, J. M.; Belier, G.; Girod, M.; Goutte, H.; Meot, V.; Perru, O.; Roig, O.; Sauvestre, J. E.; Sawicka, M.; Pfuetzner, M.; Zylicz, J.; Matea, I.; Giovinazzo, J.; Grawe, H.; Becker, F.; Mayet, P.; Grzywacz, R.; Achouri, N. L.; Angelique, J. C.; Baiborodin, D.

    2006-01-01

    An island of isomers have recently been observed on both sides of the N=40 shell below the Ni isotopes. Isomeric states in the 65Fe and 67Fe allow the knowledge of the single particle structure around the νg9/2 shell. Moreover, the excitation energy of the first 2+ and 4+ states in the 68Fe have been established by β-γ correlation. The evolution of the structure of the Fe isotopes going far away from the valley of stability is, for the first time, given for N>40

  19. Stochastic Equilibria under Imprecise Deviations in Terminal-Reward Concurrent Games

    Directory of Open Access Journals (Sweden)

    Patricia Bouyer

    2016-09-01

    Full Text Available We study the existence of mixed-strategy equilibria in concurrent games played on graphs. While existence is guaranteed with safety objectives for each player, Nash equilibria need not exist when players are given arbitrary terminal-reward objectives, and their existence is undecidable with qualitative reachability objectives (and only three players. However, these results rely on the fact that the players can enforce infinite plays while trying to improve their payoffs. In this paper, we introduce a relaxed notion of equilibria, where deviations are imprecise. We prove that contrary to Nash equilibria, such (stationary equilibria always exist, and we develop a PSPACE algorithm to compute one.

  20. Stability of equilibria for a two-phase osmosis model

    NARCIS (Netherlands)

    Lippoth, F.; Prokert, G.

    2012-01-01

    For a two-phase moving boundary problem modelling the motion of a semipermeable membrane by osmotic pressure and surface tension, we prove that the manifold of equilibria is locally exponentially attractive. Our method relies on maximal regularity results for parabolic systems with relaxation type

  1. A Numerical Algorithm to find All Scalar Feedback Nash Equilibria

    NARCIS (Netherlands)

    Engwerda, J.C.

    2013-01-01

    Abstract: In this note we generalize a numerical algorithm presented in [9] to calculate all solutions of the scalar algebraic Riccati equations that play an important role in finding feedback Nash equilibria of the scalar N-player linear affine-quadratic differential game. The algorithm is based on

  2. Computing Proper Equilibria of Zero-Sum Games

    DEFF Research Database (Denmark)

    Miltersen, Peter Bro; Sørensen, Troels Bjerre

    2007-01-01

    We show that a proper equilibrium of a matrix game can be found in polynomial time by solving a linear (in the number of pure strategies of the two players) number of linear programs of roughly the same dimensions as the standard linear programs describing the Nash equilibria of the game....

  3. Shallow-water vortex equilibria and their stability

    Energy Technology Data Exchange (ETDEWEB)

    Plotka, H; Dritschel, D G, E-mail: hanna@mcs.st-andrews.ac.uk, E-mail: dgd@mcs.st-andrews.ac.uk [School of Mathematics and Statistics, University of St Andrews, North Haugh, St. Andrews KY16 9SS (United Kingdom)

    2011-12-22

    We first describe the equilibrium form and stability of steadily-rotating simply-connected vortex patches in the single-layer quasi-geostrophic model of geophysical fluid dynamics. This model, valid for rotating shallow-water flow in the limit of small Rossby and Froude numbers, has an intrinsic length scale L{sub D} called the 'Rossby deformation length' relating the strength of stratification to that of the background rotation rate. Specifically, L{sub D} = c/f where c={radical}gH is a characteristic gravity-wave speed, g is gravity (or 'reduced' gravity in a two-layer context where one layer is infinitely deep), H is the mean active layer depth, and f is the Coriolis frequency (here constant). We next introduce ageostrophic effects by using the full shallow-water model to generate what we call 'quasi-equilibria'. These equilibria are not strictly steady, but radiate such weak gravity waves that they are steady for all practical purposes. Through an artificial ramping procedure, we ramp up the potential vorticity anomaly of the fluid particles in our quasi-geostrophic equilibria to obtain shallow-water quasi-equilibria at finite Rossby number. We show a few examples of these states in this paper.

  4. Asset pricing puzzles explained by incomplete Brownian equilibria

    DEFF Research Database (Denmark)

    Christensen, Peter Ove; Larsen, Kasper

    We examine a class of Brownian based models which produce tractable incomplete equilibria. The models are based on finitely many investors with heterogeneous exponential utilities over intermediate consumption who receive partially unspanned income. The investors can trade continuously on a finit...... markets. Consequently, our model can simultaneously help explaining the risk-free rate and equity premium puzzles....

  5. Predicting phase equilibria in one-component systems

    Science.gov (United States)

    Korchuganova, M. R.; Esina, Z. N.

    2015-07-01

    It is shown that Simon equation coefficients for n-alkanes and n-alcohols can be modeled using critical and triple point parameters. Predictions of the phase liquid-vapor, solid-vapor, and liquid-solid equilibria in one-component systems are based on the Clausius-Clapeyron relation, Van der Waals and Simon equations, and the principle of thermodynamic similarity.

  6. Field line diversion properties of finite β Helias equilibria

    International Nuclear Information System (INIS)

    Hayashi, T.; Schwenn, U.; Strumberger, E.

    1992-03-01

    The diversion properties of the magnetic field outside the last closed magnetic surface of a Helias stellarator configuration are investigated for finite β-equilibria. The results support a divertor concept which has been developed from the diversion properties of the corresponding vacuum field. Cross-field transport is simulated by a simplified scrape-off layer (SOL) model. (author)

  7. From Singularity Theory to Finiteness of Walrasian Equilibria

    DEFF Research Database (Denmark)

    Castro, Sofia B.S.D.; Dakhlia, Sami F.; Gothen, Peter

    The paper establishes that for an open and dense subset of smooth exchange economies, the number of Walrasian equilibria is finite. In particular, our results extend to non-regular economies; it even holds when restricted to the subset of critical ones. The proof rests on concepts from singularity...... theory....

  8. Close pairs of relative equilibria for identical point vortices

    DEFF Research Database (Denmark)

    Dirksen, Tobias; Aref, Hassan

    2011-01-01

    Numerical solution of the classical problem of relative equilibria for identical point vortices on the unbounded plane reveals configurations that are very close to the analytically known, centered, symmetrically arranged, nested equilateral triangles. New numerical solutions of this kind are fou...

  9. Cryptographically Blinded Games: Leveraging Players' Limitations for Equilibria and Profit

    DEFF Research Database (Denmark)

    Hubacek, Pavel; Park, Sunoo

    2014-01-01

    In this work we apply methods from cryptography to enable mutually distrusting players to implement broad classes of mediated equilibria of strategic games without trusted mediation. Our implementation uses a pre-play 'cheap talk' phase, consisting of non- binding communication between players...

  10. Xylose Isomerization with Zeolites in a Two-Step Alcohol–Water Process

    DEFF Research Database (Denmark)

    Paniagua, Marta; Shunmugavel, Saravanamurugan; Melián Rodriguez, Mayra

    2015-01-01

    Isomerization of xylose to xylulose was efficiently catalyzed by large-pore zeolites in a two-step methanol–water process that enhanced the product yield significantly. The reaction pathway involves xylose isomerization to xylulose, which, in part, subsequently reacts with methanol to form methyl...

  11. Control of structural isomerism in noncovalent hydrogen-bonded assemblies using peripheral chiral information

    NARCIS (Netherlands)

    Prins, L.J.; Jolliffe, K.A.; Hulst, A.J.R.L.; Timmerman, P.; Reinhoudt, David

    2000-01-01

    The results of a systematic study of the structural isomerism in more than 30 noncovalent hydrogen-bonded assemblies are described. These dynamic assemblies, composed of three calix[4]arene dimelamines and six barbiturates/cyanurates, can be present in three isomeric forms with either D3, C3h, or Cs

  12. Iridium-Catalyzed Dynamic Kinetic Isomerization: Expedient Synthesis of Carbohydrates from Achmatowicz Rearrangement Products.

    Science.gov (United States)

    Wang, Hao-Yuan; Yang, Ka; Bennett, Scott R; Guo, Sheng-rong; Tang, Weiping

    2015-07-20

    A highly stereoselective dynamic kinetic isomerization of Achmatowicz rearrangement products was discovered. This new internal redox isomerization provided ready access to key intermediates for the enantio- and diastereoselective synthesis of a series of naturally occurring sugars. The nature of the de novo synthesis also enables the preparation of both enantiomers. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Analysis of Optimal Process Flow Diagrams of Light Naphtha Isomerization Process by Mathematic Modelling Method

    OpenAIRE

    Chuzlov, Vyacheslav Alekseevich; Molotov, Konstantin

    2016-01-01

    An approach to simulation of hydrocarbons refining processes catalytic reactors. The kinetic and thermodynamic research of light naphtha isomerization process was conducted. The kinetic parameters of hydrocarbon feedstock chemical conversion on different types of platinum-content catalysts was established. The estimation of efficiency of including different types of isomerization technologies in oil refinery flow diagram was performed.

  14. Green Synthesis of Carvenone by Montmorillonite-Catalyzed Isomerization of 1,2-Limonene Oxide

    DEFF Research Database (Denmark)

    Nguyen, Thao-Tran Thi; Chau, Duy-Khiem Nguyen; Duus, Fritz

    2013-01-01

    Montmorillonite was considered as a good heterogeneous catalyst for the isomerization of 1,2-limonene oxide into car-venone under solvent-free condition. Both conventional heating and green activations were tested in this research. The microwave-assisted isomerization afforded carvenone in high...

  15. Analysis of Optimal Process Flow Diagrams of Light Naphtha Isomerization Process by Mathematic Modelling Method

    Directory of Open Access Journals (Sweden)

    Chuzlov Vjacheslav

    2016-01-01

    Full Text Available An approach to simulation of hydrocarbons refining processes catalytic reactors. The kinetic and thermodynamic research of light naphtha isomerization process was conducted. The kinetic parameters of hydrocarbon feedstock chemical conversion on different types of platinum-content catalysts was established. The estimation of efficiency of including different types of isomerization technologies in oil refinery flow diagram was performed.

  16. Tandem ring-closing metathesis/isomerization reactions for the total synthesis of violacein

    DEFF Research Database (Denmark)

    Petersen, Mette Terp; Nielsen, Thomas Eiland

    2013-01-01

    A series of 5-substituted 2-pyrrolidinones was synthesized through a one-pot ruthenium alkylidene-catalyzed tandem RCM/isomerization/nucleophilic addition sequence. The intermediates resulting from RCM/isomerization showed reactivity toward electrophiles in aldol condensation reactions which...

  17. On Nash-Equilibria of Approximation-Stable Games

    Science.gov (United States)

    Awasthi, Pranjal; Balcan, Maria-Florina; Blum, Avrim; Sheffet, Or; Vempala, Santosh

    One reason for wanting to compute an (approximate) Nash equilibrium of a game is to predict how players will play. However, if the game has multiple equilibria that are far apart, or ɛ-equilibria that are far in variation distance from the true Nash equilibrium strategies, then this prediction may not be possible even in principle. Motivated by this consideration, in this paper we define the notion of games that are approximation stable, meaning that all ɛ-approximate equilibria are contained inside a small ball of radius Δ around a true equilibrium, and investigate a number of their properties. Many natural small games such as matching pennies and rock-paper-scissors are indeed approximation stable. We show furthermore there exist 2-player n-by-n approximation-stable games in which the Nash equilibrium and all approximate equilibria have support Ω(log n). On the other hand, we show all (ɛ,Δ) approximation-stable games must have an ɛ-equilibrium of support O(Δ^{2-o(1)}/ɛ2{log n}), yielding an immediate n^{O(Δ^{2-o(1)}/ɛ^2log n)}-time algorithm, improving over the bound of [11] for games satisfying this condition. We in addition give a polynomial-time algorithm for the case that Δ and ɛ are sufficiently close together. We also consider an inverse property, namely that all non-approximate equilibria are far from some true equilibrium, and give an efficient algorithm for games satisfying that condition.

  18. Magnetoacoustic heating and FCT-equilibria in the belt pinch

    International Nuclear Information System (INIS)

    Erckmann, V.

    1983-02-01

    In the HECTOR belt pinch of high β plasma is produced by magnetic compression in a Tokamak geometry. After compresseion the initial β value can be varied between 0.2 and 0.8. During 5 μs the plasma is further heated by a fast magnetoacoustic wave with a frequency near the first harmonic of the ion cyclotronfrequency. For the first time the β-value of a pinch plasma could be increased further from 0.34 after compression to 0.46 at the end of the rf-heating cycle. By proper selection of the final β-value the region for resonance absorption of the heating wave can be shifted. Strong heating (200 MW) has been observed in the cases, where the resonance region has been located in the center of the plasma. In deuterium discharges an increase in ion temperature is observed during the heating process, whereas the electrons are energetically decoupled, showing no temperature increase. Strong plasma losses are found in the 200 MW range after the rf-heating process. The dominant mechanisms are charge exchange collisions with neutral gas atoms. During rf-heating and the subsequent cooling phase the magnetic flux is frozen due to the high conductivity of the plasma. The observed equilibria could be identified as flux conserving Tokamak (FCT) equilibria. Based on a two-dimensional code the time-evolution of the equilibria has been calculated. The q-profiles are time-independent, with increasing β the magnetic axis of the plasma is shifted towards the outer boundary of the torus, and finally the linear relation between β and βsub(pol), which is characteristic for low-β-equilibria, is no longer valid. Thus for the first time the existence of FCT-equilibria at high β has been demonstrated experimentally together with a qualitative agreement with FCT-theory. (orig./AH) [de

  19. Excitation functions and isomeric ratios for the isomeric pair sup(106m)Ag and sup(106g)Ag in the 107Ag (d,t) reaction

    International Nuclear Information System (INIS)

    Lalli, M.E.; Wasilevsky de Lammirato, C.; Herreros, O.R.; Nassiff, S.J.

    1976-09-01

    Excitation functions and isomeric cross section ratios have been measured for the 107 Ag (d,t), reaction in which the isomeric pair sup(106m/106g)Ag is produced. Thick-target yields have been determined for different irradiation times and as a function of deuteron energy. Stacked silver foils with aluminium foils as monitors were bombarded with deuterons up to 27 MeV and the activities of products measured with a calibrated Ge(Li) counter. (author) [es

  20. Process for paraffin isomerization of a distillate range hydrocarbon feedstock

    Energy Technology Data Exchange (ETDEWEB)

    Chen, N.Y.; Garwood, W.E.; McCullen, S.B.

    1993-01-19

    Various catalytic processes have been proposed to isomerize n-paraffins so as to lower the pour point of distillate range hydrocarbon feedstocks. However, many available feedstocks contain nitrogen impurities which tend to poison conventional paraffin isomerization catalysts. A process has been developed to obviate or alleviate this problem. According to the invention, the paraffin-containing feedstock is contacted with a crystalline aluminosilicate zeolite catalyst having pore openings defined by a ratio of sorption of n-hexane to o-xylene of over 3 vol % and the ability to crack 3-methylpentane in preference to 2,3 dimethylbutane under defined conditions. The zeolite catalyst includes a Group VIII metal and has a zeolite SiO[sub 2]/Al[sub 2]O[sub 3] ratio of at least 20:1. The contacting is carried out at 199-454 C and a pressure of 100-1,000 psig, preferably 250-600 psig. The group of medium pore zeolites which can be used in the process of the invention includes ZSM-22, ZSM-23, and ZSM-35. The Group VIII metals used in the catalyst are preferably selected from Pt, Pd, Ir, Os, Rh, and Ru and the metal is preferably incorporated into the zeolite by ion exchange up to a metal content of preferably 0.1-3 wt %. Experiments are described to illustrate the invention. 1 tab.

  1. Computational Studies of Bridging Structures and Isomerism in Substituted Disilynes.

    Science.gov (United States)

    Serafin, Lukasz M; Law, Mark M; van Mourik, Tanja

    2013-06-11

    The substituted disilyne molecules, Si2Li2 and Si2HX, where X = Li, F, and Cl, have been investigated using the high-level CCSD(T) and CCSD(T)-F12 ab initio methods. The calculations have found or confirmed the existence of several isomeric forms and transition states for each molecule. Optimized geometries, relative energies, and harmonic vibration frequencies are reported. Bridging structures exist in all cases. Comparisons are made with existing literature results for the related Si2H2, C2X2, and C2HX isomerizing systems. Additionally, CCSD(T) and CCSD(T)-F12 calculations were performed for Si2H2, for which experimental spectroscopic data are available. Results calculated with CCSD(T)-F12 and the cc-pVTZ-F12 basis set are of comparable quality as those computed with CCSD(T) and the much larger cc-pV(6+d)Z basis set, at much less computational cost. We recommend the CCSD(T)-F12/cc-pVTZ-F12 level of theory as a very attractive alternative to conventional CCSD(T).

  2. Low-lying isomeric levels in Cu75

    Science.gov (United States)

    Daugas, J. M.; Faul, T.; Grawe, H.; Pfützner, M.; Grzywacz, R.; Lewitowicz, M.; Achouri, N. L.; Angélique, J. C.; Baiborodin, D.; Bentida, R.; Béraud, R.; Borcea, C.; Bingham, C. R.; Catford, W. N.; Emsallem, A.; de France, G.; Grzywacz, K. L.; Lemmon, R. C.; Lopez Jimenez, M. J.; de Oliveira Santos, F.; Regan, P. H.; Rykaczewski, K.; Sauvestre, J. E.; Sawicka, M.; Stanoiu, M.; Sieja, K.; Nowacki, F.

    2010-03-01

    Isomeric low-lying states were identified and investigated in the Cu75 nucleus. Two states at 61.8(5)- and 128.3(7)-keV excitation energies with half-lives of 370(40)- and 170(15)-ns were assigned as Cu75m1 and Cu75m2, respectively. The measured half-lives combined with the recent spin assignment of the ground state allow one to deduce tentatively spin and parity of the two isomers and the dominant multipolarities of the isomeric transitions with respect to the systematics of the Cu isotopes. Shell-model calculations using an up-to-date effective interaction reproduce the evolution of the 1/2-, 3/2-, and 5/2- states for the neutron-rich odd-mass Cu isotopes when filling the νg9/2. The results indicate a significant change in the nuclear structure in this region, where a single-particle 5/2- state coexists with more and more collective 3/2- and 1/2- levels at low excitation energies.

  3. Destabilization in the isomeric nitrobenzonitriles: an experimental thermochemical study

    International Nuclear Information System (INIS)

    Roux, Maria Victoria; Jimenez, Pilar; Davalos, Juan Z.; Temprado, Manuel; Liebman, Joel F.

    2003-01-01

    The enthalpies of combustion and of sublimation, respectively, of the three isomeric nitrobenzonitriles have been measured: o-, {(-3456.3±2.9), (88.1±1.4)} kJ·mol -1 ; m-, {(-3442.8±3.3), (92.8±0.3)} kJ·mol -1 ; p-, {(-3448.2±3.6), (91.1±1.3)} kJ·mol -1 . In turn, from these values, the standard molar enthalpies of formation for the condensed and gaseous state, respectively, have been derived: o-, {(130.1±3.1), (218.2±3.4)} kJ·mol -1 ; m-, {(116.5±3.5), (209.3±3.5)} kJ·mol -1 ; p-, {(122.0±3.8), (213.1±4.0)} kJ·mol -1 . Destabilization energies associated with the presence of the two electron-withdrawing groups have been determined, for o-, m-, and p-nitrobenzonitrile, {(17.6±4.1), (8.7±4.2), and (12.5±4.6)} kJ·mol -1 , respectively, and are consistent with those obtained for the corresponding sets of isomeric methyl benzenedicarboxylates, dicyanobenzenes, dinitrobenzenes, and (neutral and ionized) nitrobenzoic acids

  4. Catalyst compositions useful for olefin isomerization and disproportionation

    International Nuclear Information System (INIS)

    Drake, C.A.

    1987-01-01

    A process is described for the double bond isomerization of an aliphatic olefinic hydrocarbon feed which comprises contacting the feed under isomerization conditions with a catalyst prepared by: (a) impregnating an alumina support having a surface area of at least 200 m/sup 2//g and a pore volume of at least 0.45 cm/sup 3//g with: 1 up to 20 wt. % of at least one magnesium compound convertible to the oxide, based on the weight of support and calculated as the metal; 0 up to 5 wt. % of at least one alkali metal compound convertible to the oxide, based on the weight of support and calculated as the metal; and 0 up to 5 wt. % of at least one zirconium compound convertible to the oxide, based on the weight of support and calculated as the metal; and (b) heating the alumina support impregnated in accordance with step (a) in an oxygen-containing atmosphere under conditions suitable to convert at least a portion of the magnesium, alkali metal, and zirconium compounds to the oxide form

  5. β-γ and isomeric decay spectroscopy of 168Dy

    Directory of Open Access Journals (Sweden)

    Zhang G.X.

    2018-01-01

    Full Text Available This contribution will report on the experimental work on the level structure of 168Dy. The experimental data have been taken as part of the EURICA decay spectroscopy campaign at RIBF, RIKEN in November 2014. In the experiment, a 238U primary beam is accelerated up to 345 MeV/u with an average intensity of 12 pnA. The nuclei of interest are produced by in-flight fission of 238U impinging on Be target with a thickness of 5 mm. The excited states of 168Dy have been populated through the decay from a newly identified isomeric state and via the β decay from 168Tb. In this contribution, scientific motivations, experimental procedure and some preliminary results for this study are presented.

  6. β-γ and isomeric decay spectroscopy of 168Dy

    Science.gov (United States)

    Zhang, G. X.; Watanabe, H.; Kondev, F. G.; Lane, G. J.; Regan, P. H.; Söderström, P.-A.; Walker, P. M.; Kanaoka, H.; Korkulu, Z.; Lee, P. S.; Liu, J. J.; Nishimura, S.; Wu, J.; Yagi, A.; Ahn, D. S.; Alharbi, T.; Baba, H.; Browne, F.; Bruce, A. M.; Carroll, R. J.; Chae, K. Y.; Dombradi, Zs.; Doornenbal, P.; Estrade, A.; Fukuda, N.; Griffin, C.; Ideguchi, E.; Inabe, N.; Isobe, T.; Kanaya, S.; Kojouharov, I.; Kubo, T.; Kubono, S.; Kurz, N.; Kuti, I.; Lalkovski, S.; Lee, C. S.; Lee, E. J.; Lorusso, G.; Lotay, G.; Moon, C.-B.; Nishizuka, I.; Nita, C. R.; Odahara, A.; Patel, Z.; Phong, V. H.; Podolyák, Zs.; Roberts, O. J.; Sakurai, H.; Schaffner, H.; Shand, C. M.; Shimizu, Y.; Sumikama, T.; Suzuki, H.; Takeda, H.; Terashima, S.; Vajta, Zs.; Valiente-Dóbon, J. J.; Xu, Z. Y.

    2018-05-01

    This contribution will report on the experimental work on the level structure of 168Dy. The experimental data have been taken as part of the EURICA decay spectroscopy campaign at RIBF, RIKEN in November 2014. In the experiment, a 238U primary beam is accelerated up to 345 MeV/u with an average intensity of 12 pnA. The nuclei of interest are produced by in-flight fission of 238U impinging on Be target with a thickness of 5 mm. The excited states of 168Dy have been populated through the decay from a newly identified isomeric state and via the β decay from 168Tb. In this contribution, scientific motivations, experimental procedure and some preliminary results for this study are presented.

  7. Sloshing-ion equilibria in the TARA endplugs

    International Nuclear Information System (INIS)

    Hokin, S.; Kesner, J.

    1983-11-01

    We have employed a modified version of the LLNL Bounce-average Fokker-Planck code to model neutral beam-produced sloshing-ion equilibria in the TARA endplugs. The questions we have addressed concern the effect of deuterium beam operation as opposed to hydrogen operation, and the advantage of using full-energy beams rather than the usual three-component beams. We find that, for the expected base case TARA operating parameters, a 40% savings in required beam power is attained by using deuterium beams rather than hydrogen beams, and that the use of full-energy beams results in an additional 26% power savings for these parameters. For higher plasma temperatures the use of full-energy beams becomes significantly advantagous. We have also investigated the equilibria of two possible alternate mirror configurations for the TARA endplugs, believed to be more stable to trapped particle modes, and report those results here

  8. Phase diagrams and heterogeneous equilibria a practical introduction

    CERN Document Server

    Predel, Bruno; Pool, Monte

    2004-01-01

    This graduate-level textbook provides an introduction to the practical application of phase diagrams. It is intended for students and researchers in chemistry, metallurgy, mineralogy, and materials science as well as in engineering and physics. Heterogeneous equilibria are described by a minimum of theory illustrated by practical examples and realistic case discussions from the different fields of application. The treatment of the physical and energetic background of phase equilibria leads to the discussion of the thermodynamics of mixtures and the correlation between energetics and composition. Thus, tools for the prediction of energetic, structural, and physical quantities are provided. The authors treat the nucleation of phase transitions, the production and stability of technologically important metastable phases, and metallic glasses. Furthermore, the text also concisely presents the thermodynamics and composition of polymer systems.

  9. Extended Group Contribution Model for Polyfunctional Phase Equilibria

    DEFF Research Database (Denmark)

    Abildskov, Jens

    of physical separation processes. In a thermodynamic sense, design requires detailed knowledge of activity coefficients in the phases at equilibrium. The prediction of these quantities from a minimum of experimental data is the broad scope of this thesis. Adequate equations exist for predicting vapor......Material and energy balances and equilibrium data form the basis of most design calculations. While material and energy balances may be stated without much difficulty, the design engineer is left with a choice between a wide variety of models for describing phase equilibria in the design......-liquid equilibria from data on binary mixtures, composed of structurally simple molecules with a single functional group. More complex is the situation with mixtures composed of structurally more complicated molecules or molecules with more than one functional group. The UNIFAC method is extended to handle...

  10. Theoretical study of isomerization and decomposition of propenal

    International Nuclear Information System (INIS)

    Chin, Chih-Hao; Lee, Shih-Huang

    2011-01-01

    We investigated the dynamics of isomerization and multi-channel dissociation of propenal (CH 2 CHCHO), methyl ketene (CH 3 CHCO), hydroxyl propadiene (CH 2 CH 2 CHOH), and hydroxyl cyclopropene (cyclic-C 3 H 3 -OH) in the ground potential-energy surface using quantum-chemical calculations. Optimized structures and vibrational frequencies of molecular species were computed with method B3LYP/6-311G(d,p). Total energies of molecules at optimized structures were computed at the CCSD(T)/6-311+G(3df,2p) level of theory. We established the potential-energy surface for decomposition to CH 2 CHCO + H, CH 2 CH + HCO, CH 2 CH 2 /CH 3 CH + CO, CHCH/CH 2 C + H 2 CO, CHCCHO/CH 2 CCO + H 2 , CHCH + CO + H 2 , CH 3 + HCCO, CH 2 CCH + OH, and CH 2 CC/cyclic-C 3 H 2 + H 2 O. Microcanonical rate coefficients of various reactions of trans-propenal with internal energies 148 and 182 kcal mol -1 were calculated using Rice-Ramsperger-Kassel-Marcus and Variational transition state theories. Product branching ratios were derivable using numerical integration of kinetic master equations and the steady-state approximation. The concerted three-body dissociation of trans-propenal to fragments C 2 H 2 + CO + H 2 is the prevailing channel in present calculations. In contrast, C 3 H 3 O + H, C 2 H 3 + HCO and C 2 H 4 + CO were identified as major channels in the photolysis of trans-propenal. The discrepancy between calculations and experiments in product branching ratios indicates that the three major photodissociation channels occur mainly on an excited potential-energy surface whereas the other channels occur mainly on the ground potential-energy surface. This work provides profound insight in the mechanisms of isomerization and multichannel dissociation of the system C 3 H 4 O.

  11. Ti-Catalyzed Selective Isomerization of Terminal Mono-substituted Olefins

    International Nuclear Information System (INIS)

    Lee, Hyung Soo; Lee, Gab Yong

    2005-01-01

    The isomerization of olefins occurs either by a metal hydride addition-elimination or by a π-allyl metal hydride intermediate. HCo(CO) 4 , [(C 2 H 4 ) 2 RhCl] 2 , Ni[P(OEt) 3 ] 4 , and PtCl 2 (PPh 3 ) 2 -SnCl 2 are effective catalysts for isomerization of olefins via a metal hydride addition-elimination mechanism, 3,4 and Fe 3 (CO) 12 catalyzed isomerization of 3-ethyl-1-pentene and isomerization of 1-heptene catalyzed by (PhCN) 2 PdCl 2 occur via a π-allyl metal hydride mechanism. The cis/trans ratio of 2-butene obtained from isomerization of 1-butene by RhH(CO)(PPh 3 ) 3 has also been investigated. The skeletal isomerization of olefins catalyzed by (R 3 P) 2 NiCl 2 is developed such as conversion of cis-1,4-hexadiene to trans-2-methyl-1,3-pentadiene. Titanium complexes serve as an effective catalysts for a variety of reactions such as hydroalumination, hydroboration, and hydrogenation of unsaturated hydrocarbons. We have been interested in the selective reactions of unsaturated hydrocarbons by using titanium and zirconium compounds. The reagent system composed of LiAlH 4 /Cp 2 TiCl 2 ≤ 2 in the molar ratio promotes the isomerization of 1-octene, but the detailed reaction for isomerization of olefins has not been reported. We report here a selective isomerization of olefins with low valent titanium complex generated from Cp 2 TiCl 2 (Cp=cyclopentadienyl) and LiAlH 4

  12. Magnetic coordinates for equilibria with a continuous symmetry

    International Nuclear Information System (INIS)

    Dewar, R.L.; Monticello, D.A.; Sy, W.N.C.

    1983-08-01

    Magnetic coordinates for hydromagnetic equilibria are defined which treat toroidal and straight helical plasmas equivalently yet exploit the existence of a continuous symmetry to derive relations between various geometrical and physical quantities. This allows the number of equilibrium quantities which must be known to be reduced to a minimal, or primitive set. Practical formulae for various quantities required in hydromagnetic stability calculations (interchange, ballooning, and global) are given in terms of this primitive set

  13. Phase equilibria and phase structures of polymer blends

    International Nuclear Information System (INIS)

    Chalykh, Anatolii E; Gerasimov, Vladimir K

    2004-01-01

    Experimental, methodical and theoretical studies dealing with phase equilibria and phase structures of polymer blends are generalised. The general and specific features of the change in solubility of polymers with changes in the molecular mass and copolymer composition and upon the formation of three-dimensional cross-linked networks are described. The results of the effect of the prehistory on the phase structure and the non-equilibrium state of polymer blends are considered in detail.

  14. Existence of equilibria in quantum Bertrand-Edgeworth duopoly game

    Science.gov (United States)

    Sekiguchi, Yohei; Sakahara, Kiri; Sato, Takashi

    2012-12-01

    Both classical and quantum version of two models of price competition in duopoly market, the one is realistic and the other is idealized, are investigated. The pure strategy Nash equilibria of the realistic model exists under stricter condition than that of the idealized one in the classical form game. This is the problem known as Edgeworth paradox in economics. In the quantum form game, however, the former converges to the latter as the measure of entanglement goes to infinity.

  15. Variational-moment method for computing magnetohydrodynamic equilibria

    International Nuclear Information System (INIS)

    Lao, L.L.

    1983-08-01

    A fast yet accurate method to compute magnetohydrodynamic equilibria is provided by the variational-moment method, which is similar to the classical Rayleigh-Ritz-Galerkin approximation. The equilibrium solution sought is decomposed into a spectral representation. The partial differential equations describing the equilibrium are then recast into their equivalent variational form and systematically reduced to an optimum finite set of coupled ordinary differential equations. An appropriate spectral decomposition can make the series representing the solution coverge rapidly and hence substantially reduces the amount of computational time involved. The moment method was developed first to compute fixed-boundary inverse equilibria in axisymmetric toroidal geometry, and was demonstrated to be both efficient and accurate. The method since has been generalized to calculate free-boundary axisymmetric equilibria, to include toroidal plasma rotation and pressure anisotropy, and to treat three-dimensional toroidal geometry. In all these formulations, the flux surfaces are assumed to be smooth and nested so that the solutions can be decomposed in Fourier series in inverse coordinates. These recent developments and the advantages and limitations of the moment method are reviewed. The use of alternate coordinates for decomposition is discussed

  16. (Liquid + liquid) equilibria of perfluorocarbons with fluorinated ionic liquids

    International Nuclear Information System (INIS)

    Martinho, S.; Araújo, J.M.M.; Rebelo, L.P.N.; Pereiro, A.B.; Marrucho, I.M.

    2013-01-01

    Highlights: • (Liquid + liquid) equilibria perfluorocarbons and fluorinated ionic liquids. • Non-Random Two Liquid model was successfully applied. • Thermodynamic functions that describe the solvation process were calculated. -- Abstract: In order to evaluate the feasibility of partially replace perfluorocarbons (PFCs) with fluorinated ionic liquids (FILs) in PFCs-in-water emulsions, usually used for biomedical purposes, herein the (liquid + liquid) phase equilibria of FILs containing fluorinated chains longer than four carbons with PFCs were carried out in a wide range of temperatures. With this goal in mind, two PFCs (perfluorooctane and perfluorodecalin) were selected and the (liquid + liquid) equilibria of the binary mixtures of these PFCs and FILs were studied at atmospheric pressure in a temperature range from T (293.15 to 343.15) K. For these studies, FILs containing ammonium, pyridinium and imidazolium cations and different anions with fluorocarbon alkyl chains between 4 and 8 were included. Additionally, Non-Random Two Liquid (NRTL) thermodynamic model was successfully applied to correlate the behaviour of the PFCs + FILs binary mixtures. Moreover, thermodynamic functions that describe the solvation process were calculated from the experimental data

  17. Long-term Nash equilibria in electricity markets

    International Nuclear Information System (INIS)

    Pozo, David; Contreras, Javier; Caballero, Angel; de Andres, Antonio

    2011-01-01

    In competitive electricity markets, companies simultaneously offer their productions to obtain the maximum profits on a daily basis. In the long run, the strategies utilized by the electric companies lead to various long-term equilibria that can be analyzed with the appropriate tools. We present a methodology to find plausible long-term Nash equilibria in pool-based electricity markets. The methodology is based on an iterative market Nash equilibrium model in which the companies can decide upon their offer strategies. An exponential smoothing of the bids submitted by the companies is applied to facilitate the convergence of the iterative procedure. In each iteration of the model the companies face residual demand curves that are accurately modeled by Hermite interpolating polynomials. We introduce the concept of meta-game equilibrium strategies to allow companies to have a range of offer strategies where several pure and mixed meta-game Nash equilibria are possible. With our model it is also possible to model uncertainty or to generate price scenarios for financial models that assess the value of a generating unit by real options analysis. The application of the proposed methodology is illustrated with several realistic case studies. (author)

  18. Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols.

    Science.gov (United States)

    Larionov, Evgeny; Lin, Luqing; Guénée, Laure; Mazet, Clément

    2014-12-03

    Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.

  19. New isomeric states in 152,154,156Nd produced by spontaneous fission of 252Cf

    International Nuclear Information System (INIS)

    Gautherin, C.; Houry, M.; Korten, W.; Le Coz, Y.; Lucas, R.; Phan, X.H.; Theisen, C.; Belier, G.; Girod, M.; Meot, V.; Peru, S.; Astier, A.; Ducroux, L.; Meyer, M.; Redon, N.

    1998-01-01

    Isomeric states have been observed in fission-fragments produced by spontaneous fission of 252 Cf. These states are found in neutron rich nuclei of different structure and deformations. About 50 isomeric nuclei have been observed using coincidences between γ-rays identified in EUROGAM II and fission fragments detected in photovoltaic cells (SAPhIR). Lifetimes in the range from 20 ns to 2μs have been measured. Presented calculations based on HFB+D1S force on new measured isomeric states in the 152,154,156 Nd show evidence for K-isomers. (orig.)

  20. Isomerization of glucose into fructose by environmentally friendly Fe/β zeolite catalysts.

    Science.gov (United States)

    Xu, Siquan; Zhang, Lei; Xiao, Kehao; Xia, Haian

    2017-06-29

    Herein, the environmentally friendly Fe/β zeolite for glucose isomerization to fructose in aqueous media was reported for the first time. The effects of various reaction conditions including reaction temperature, reaction time, catalyst dosage, etc. on the isomerization reaction over Fe/β zeolite were studied in detail. Under the optimized conditions, yield of fructose higher than 20% were obtained. Moreover, the Fe/β zeolite catalysts were stable and remained constant catalytic activity after five consecutive runs. The possible active Fe species for isomerization of glucose in Fe/β zeolite is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. The Pierce diode with an external circuit. I. Oscillations about nonuniform equilibria

    International Nuclear Information System (INIS)

    Lawson, W.S.

    1989-01-01

    The nonuniform (nonlinear) equilibria of the classical (short circuit) Pierce diode and the extended (series RLC external circuit) Pierce diode are described, and the spectrum of oscillations (stable and unstable) about these equilibria are worked out. It is found that only the external capacitance alters the equilibria, though all elements alter the spectrum. In particular, the introduction of an external capacitor destabilizes some equilibria that are marginally stable without the capacitor. Computer simulations are performed to test the theoretical predictions for the case of an external capacitor only. It is found that most equilibria are correctly predicted by theory, but that the continuous set of equilibria of the classical Pierce diode at Pierce parameters (α=ω/sub pL//v 0 ) that are multiples of 2π are not observed. This appears to be a failure of the simulation method under the rather singular conditions rather than a failure of the theory

  2. Stability and attractive basins of multiple equilibria in delayed two-neuron networks

    International Nuclear Information System (INIS)

    Huang Yu-Jiao; Zhang Hua-Guang; Wang Zhan-Shan

    2012-01-01

    Multiple stability for two-dimensional delayed recurrent neural networks with piecewise linear activation functions of 2r (r ≥ 1) corner points is studied. Sufficient conditions are established for checking the existence of (2r + 1) 2 equilibria in delayed recurrent neural networks. Under these conditions, (r + 1) 2 equilibria are locally exponentially stable, and (2r + 1) 2 — (r + 1) 2 — r 2 equilibria are unstable. Attractive basins of stable equilibria are estimated, which are larger than invariant sets derived by decomposing state space. One example is provided to illustrate the effectiveness of our results. (general)

  3. The Pierce diode with an external circuit: II, Non-uniform equilibria

    International Nuclear Information System (INIS)

    Lawson, W.S.

    1987-01-01

    The non-uniform (non-linear) equilibria of the classical (short circuit) Pierce diode and the extended (series RLC external circuit) Pierce diode are described theoretically, and explored via computer simulation. It is found that most equilibria are correctly predicted by theory, but that the continuous set of equilibria of the classical Pierce diode at α = 2π are not observed. The stability characteristics of the non-uniform equilibria are also worked out, and are consistent with the simulations. 8 refs., 22 figs., 3 tabs

  4. Intrinsic acid-base properties of a hexa-2'-deoxynucleoside pentaphosphate, d(ApGpGpCpCpT): neighboring effects and isomeric equilibria.

    Science.gov (United States)

    Domínguez-Martín, Alicia; Johannsen, Silke; Sigel, Astrid; Operschall, Bert P; Song, Bin; Sigel, Helmut; Okruszek, Andrzej; González-Pérez, Josefa María; Niclós-Gutiérrez, Juan; Sigel, Roland K O

    2013-06-17

    The intrinsic acid-base properties of the hexa-2'-deoxynucleoside pentaphosphate, d(ApGpGpCpCpT) [=(A1∙G2∙G3∙C4∙C5∙T6)=(HNPP)⁵⁻] have been determined by ¹H NMR shift experiments. The pKa values of the individual sites of the adenosine (A), guanosine (G), cytidine (C), and thymidine (T) residues were measured in water under single-strand conditions (i.e., 10% D₂O, 47 °C, I=0.1 M, NaClO₄). These results quantify the release of H⁺ from the two (N7)H⁺ (G∙G), the two (N3)H⁺ (C∙C), and the (N1)H⁺ (A) units, as well as from the two (N1)H (G∙G) and the (N3)H (T) sites. Based on measurements with 2'-deoxynucleosides at 25 °C and 47 °C, they were transferred to pKa values valid in water at 25 °C and I=0.1 M. Intramolecular stacks between the nucleobases A1 and G2 as well as most likely also between G2 and G3 are formed. For HNPP three pKa clusters occur, that is those encompassing the pKa values of 2.44, 2.97, and 3.71 of G2(N7)H⁺, G3(N7)H⁺, and A1(N1)H⁺, respectively, with overlapping buffer regions. The tautomer populations were estimated, giving for the release of a single proton from five-fold protonated H₅(HNPP)(±) , the tautomers (G2)N7, (G3)N7, and (A1)N1 with formation degrees of about 74, 22, and 4%, respectively. Tautomer distributions reveal pathways for proton-donating as well as for proton-accepting reactions both being expected to be fast and to occur practically at no "cost". The eight pKa values for H₅(HNPP)(±) are compared with data for nucleosides and nucleotides, revealing that the nucleoside residues are in part affected very differently by their neighbors. In addition, the intrinsic acidity constants for the RNA derivative r(A1∙G2∙G3∙C4∙C5∙U6), where U=uridine, were calculated. Finally, the effect of metal ions on the pKa values of nucleobase sites is briefly discussed because in this way deprotonation reactions can easily be shifted to the physiological pH range. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Direct Measurement of the Isomerization Barrier of the Isolated Retinal Chromophore

    DEFF Research Database (Denmark)

    Dilger, Jonathan; Musbat, Lihi; Sheves, Mordechai

    2015-01-01

    Isomerizations of the retinal chromophore were investigated using the IMS-IMS technique. Four different structural features of the chromophore were observed, isolated, excited collisionally, and the resulting isomer and fragment distributions were measured. By establishing the threshold activatio...

  6. Glucose Isomerization by Enzymes and Chemo-catalysts: Status and Current Advances

    DEFF Research Database (Denmark)

    Li, Hu; Yang, Song; Saravanamurugan, Shunmugavel

    2017-01-01

    of isomerization of aldoses in terms of yields, catalysts, solvents, catalytic systems, etc., by both enzymatic and chemo-catalytic approaches. Among aldose ketose interconversion reactions, fructose production by glucose isomerization to make high-fructose corn syrup (HFCS) is an industrially important and large....../intermediate fructose. This review focuses on how both enzyme and chemo-catalysts are being useful for the isomerization of glucose to fructose. Specifically, development of Lewis acid containing zeolites for glucose isomerization is reviewed in detail, including mechanism, isotopic labeling, and computational studies....... biocatalytic process today, and a large number of studies have been reported on the process development. In parallel, also alternative chemo-catalytic systems have emerged, as enzymatic conversion has drawbacks, though they are typically more selective and produce fructose under mild reaction conditions...

  7. Mechanistic features of isomerizing alkoxycarbonylation of methyl oleate

    KAUST Repository

    Roesle, Philipp

    2012-10-24

    The weakly coordinated triflate complex [(P̂P)Pd(OTf)] +(OTf)- (1) (P̂P = 1,3-bis(di-tert- butylphosphino)propane) is a suitable reactive precursor for mechanistic studies of the isomerizing alkoxcarbonylation of methyl oleate. Addition of CH 3OH or CD3OD to 1 forms the hydride species [(P ̂P)PdH(CH3OH)]+(OTf)- (2-CH3OH) or the deuteride [(P̂P)PdD(CD 3OD)]+(OTf)- (2D-CD3OD), respectively. Further reaction with pyridine cleanly affords the stable and isolable hydride [(P̂P)PdH(pyridine)]+(OTf) - (2-pyr). This complex yields the hydride fragment free of methanol by abstraction of pyridine with BF3OEt2, and thus provides an entry to mechanistic observations including intermediates reactive toward methanol. Exposure of methyl oleate (100 equiv) to 2D-CD 3OD resulted in rapid isomerization to the thermodynamic isomer distribution, 94.3% of internal olefins, 5.5% of α,β-unsaturated ester and <0.2% of terminal olefin. Reaction of 2-pyr/BF3OEt 2 with a stoichiometric amount of 1-13C-labeled 1-octene at -80 °C yields a 50:50 mixture of the linear alkyls [(P ̂P)Pd13CH2(CH2) 6CH3]+ and [(P̂P)PdCH 2(CH2)6 13CH3] + (4a and 4b). Further reaction with 13CO yields the linear acyls [(P̂P)Pd13C(=O)12/13CH 2(CH2)6 12/13CH3(L)] + (5-L; L = solvent or 13CO). Reaction of 2-pyr/BF 3·OEt2 with a stoichiometric amount of methyl oleate at -80 °C also resulted in fast isomerization to form a linear alkyl species [(P̂P)PdCH2(CH2) 16C(=O)OCH3]+ (6) and a branched alkyl stabilized by coordination of the ester carbonyl group as a four membered chelate [(P̂P)PdCH{(CH2)15CH 3}C(=O)OCH3]+ (7). Addition of carbon monoxide (2.5 equiv) at -80 °C resulted in insertion to form the linear acyl carbonyl [(P̂P)PdC(=O)(CH2)17C(=O)OCH 3(CO)]+ (8-CO) and the five-membered chelate [(P ̂P)PdC(=O)CH{(CH2)15CH3}C(=O) OCH3]+ (9). Exposure of 8-CO and 9 to 13CO at -50 °C results in gradual incorporation of the 13C label. Reversibility of 7 + CO ⇄ 9 is also evidenced by ΔG = -2.9 kcal mol-1 and

  8. Effects of alkali or acid treatment on the isomerization of amino acids.

    Science.gov (United States)

    Ohmori, Taketo; Mutaguchi, Yuta; Doi, Katsumi; Ohshima, Toshihisa

    2012-10-01

    The effect of alkali treatment on the isomerization of amino acids was investigated. The 100×D/(D+L) values of amino acids from peptide increased with increase in the number of constituent amino acid residues. Furthermore, the N-terminal amino acid of a dipeptide was isomerized to a greater extent than the C-terminal residue. Copyright © 2012. Published by Elsevier B.V.

  9. Thermal decomposition and isomerization of cis-permethrin and beta-cypermethrin in the solid phase.

    Science.gov (United States)

    González Audino, Paola; Licastro, Susana A; Zerba, Eduardo

    2002-02-01

    The stability to heart of cis-permethrin and beta-cypermethrin in the solid phase was studied and the decomposition products identified. Samples heated at 210 degrees C in an oven in the dark showed that, in the absence of potassium chlorate (the salt present in smoke-generating formulations of these pyrethroids), cis-permethrin was not isomerized, although in the presence of that salt, decomposition was greater and thermal isomerization occurred. Other salts of the type KXO3 or NaXO3, with X being halogen or nitrogen, also led to a considerable thermal isomerization. Heating the insecticides in solution in the presence of potassium chlorate did not produce isomerization in any of the solvents assayed. Salt-catalysed thermal cis-trans isomerization was also found for other pyrethroids derived from permethrinic or deltamethrinic acid but not for those derived from chrysanthemic acid. The main thermal degradation processes of cis-permethrin and beta-cypermethrin decomposition when potassium chlorate was present were cyclopropane isomerization, ester cleavage and subsequent oxidation of the resulting products. Permethrinic acid, 3-phenoxybenzyle chloride, alcohol, aldehyde and acid were identified in both cases, as well as 3-phenoxybenzyl cyanide from beta-cypermethrin. A similar decomposition pattern occurred after combustion of pyrethroid fumigant formulations.

  10. Molecular and excited state properties of isomeric scarlet disperse dyes

    Science.gov (United States)

    Lim, Jihye; Szymczyk, Malgorzata; Mehraban, Nahid; Ding, Yi; Parrillo-Chapman, Lisa; El-Shafei, Ahmed; Freeman, Harold S.

    2018-06-01

    This work was part of an investigation aimed at characterizing the molecular and excited state properties of currently available disperse dyes developed to provide stability to extensive sunlight exposures when adsorbed on poly(ethylene terephthalate) (PET) fibers. Having completed the characterization of yellow, magenta, and cyan disperse dyes for PET-based fabrics used outdoors, our attention turned to the colors designed to enhance the color gamut of a standard 4-member (cyan/yellow/magenta/black) color set. The present study pertained specifically to the characterization of commercially available scarlet dyes. In this regard, HPLC analysis showed that a scarlet product used for PET coloration was mainly a 70/30 mixture of dyes, and the use of HRMS and single crystal X-ray diffraction analyses indicated that these two dyes were azo compounds derived from isomeric pyridine-based couplers which differed in the location of the primary amino (sbnd NH2) and anilino (sbnd NHPh) groups attached to the pyridine ring. One dye structure has the sbnd NHPh group para to the azo group (Sc2), while the other has that group in the ortho position (Sc3). The presence of either ortho substituent provides photostabilization through intramolecular H-bonding with the azo moiety. Further, results from molecular modeling studies showed that the lower excited state oxidation potential of Sc3 relative to that of Sc2 allows Sc3 to function as an energy quencher for the excited state of Sc2 - through thermodynamically favorable electron transfer.

  11. Isomeric shift compensation when using resonance detectors in Moessbauer spectroscopy

    International Nuclear Information System (INIS)

    Irkaev, S.M.; Semenkin, V.A.; Sokolov, M.M.

    1981-01-01

    Method for compensation of isomeric shift of lines observed during operation of resonance detectors being part of spectrometers of nuclear gamma resonance is suggested. A flowsheet of device permitting to realize the method described is given. The method is based on using the Doppler effect. A source of resonance radiation is moved at a constant velocity, which is choosen so as to compensate energy shift of lines of the source and convertors of the resonance detector. The absorber under investigation is put in motion with a constant acceleration. The resonance detector signals are amplified selected according to amplitude by a discriminator and come to the input of multichannel analyzer operating in the regime of subsequent scaling. Analysis of experimental spectra obtained at velocities of source movement from 0 to +3 mm/s shows that value of resonance absorption effect drops as increasing energy shift in the source-converter system. It is concluded that application of the method described will permit to considerably extend the field of application of resonance detectors in the Moessbauer spectroscopy and investigate in practice all the isotopes having converted transitions [ru

  12. Computation of multi-region relaxed magnetohydrodynamic equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Hudson, S. R.; Lazerson, S. [Princeton Plasma Physics Laboratory, P.O. Box 451, Princeton, New Jersey 08543 (United States); Dewar, R. L.; Dennis, G.; Hole, M. J.; McGann, M.; Nessi, G. von [Plasma Research Laboratory, Research School of Physics and Engineering, Australian National University, Canberra ACT 0200 (Australia)

    2012-11-15

    We describe the construction of stepped-pressure equilibria as extrema of a multi-region, relaxed magnetohydrodynamic (MHD) energy functional that combines elements of ideal MHD and Taylor relaxation, and which we call MRXMHD. The model is compatible with Hamiltonian chaos theory and allows the three-dimensional MHD equilibrium problem to be formulated in a well-posed manner suitable for computation. The energy-functional is discretized using a mixed finite-element, Fourier representation for the magnetic vector potential and the equilibrium geometry; and numerical solutions are constructed using the stepped-pressure equilibrium code, SPEC. Convergence studies with respect to radial and Fourier resolution are presented.

  13. Helically symmetric equilibria with pressure anisotropy and incompressible plasma flow

    Science.gov (United States)

    Evangelias, A.; Kuiroukidis, A.; Throumoulopoulos, G. N.

    2018-02-01

    We derive a generalized Grad-Shafranov equation governing helically symmetric equilibria with pressure anisotropy and incompressible flow of arbitrary direction. Through the most general linearizing ansatz for the various free surface functions involved therein, we construct equilibrium solutions and study their properties. It turns out that pressure anisotropy can act either paramegnetically or diamagnetically, the parallel flow has a paramagnetic effect, while the non-parallel component of the flow associated with the electric field has a diamagnetic one. Also, pressure anisotropy and flow affect noticeably the helical current density.

  14. Ideal MHD stability of high poloidal beta equilibria in TFTR

    International Nuclear Information System (INIS)

    Sabbagh, S.A.; Mauel, M.E.; Navratil, G.A.; Bell, M.G.; Budny, R.V.; Chance, M.S.; Fredrickson, E.D.; Jardin, S.C.; Manickam, J.; McCune, D.C.; McGuire, K.M.; Wieland, R.M.; Zarnstorff, M.C.; Phillips, M.W.; Hughes, M.H.; Kesner, J.

    1991-01-01

    Recent experiments in TFTR have expanded the operating space of the device to include plasmas with values of var-epsilon β p dia ≡ 2μ 0 var-epsilon perpendicular >/ p >> 2 as large as 1.6, and Troyon normalized diamagnetic beta β N dia ≡ β t perpendicular aB t /10 -8 I p as large as 4.7. At values of var-epsilon β p dia ≥ 1.3, a separatrix was observed to enter the vacuum vessel, producing a naturally diverted discharge. Plasmas with large values of var-epsilon β p dia were created with both the plasma current, I p , held constant and with I p decreased, or ramped down, before the start of neutral beam injection. A convenient characterization of the change in I p using experimental parameters can be defined by the ratio of I p before the ramp down, to I p during the neutral beam heating phase, F I p . The ideal MHD stability of these equilibria is investigated to determine their location in stability space, and to study the role of plasma current and pressure profile modification in the creation of these high var-epsilon β p and β N plasmas. The evolution of these plasmas is modelled from experimental data using the TRANSP code. Two-dimensional equilibria are computed from the TRANSP results and used as input to both high and low-n stability codes including PEST. The high var-epsilon β p equilibria, which generally have an oblate cross-sectional shape, are in the first stability region to high-n ballooning modes. At constant I p , these equilibria generally have maximum pressure gradients near the magnetic axis and are stable to n=1 modes without a stabilizing conducting wall. The effect of the current profile shape on the stability of low-n kink/ballooning modes and the requirements for these plasmas to access the second stability region are examined. 6 refs

  15. Phase Equilibria Relationships of High-Tc Superconductors

    International Nuclear Information System (INIS)

    Wong-Ng, Winnie

    2011-01-01

    As an integral part of a R and D program partially supported by the Electricity Delivery and Energy Reliability Office of DOE, we have determined phase equilibria data and phase diagrams for the three generations of superconductor materials: 1st generation, (Bi,Pb)-Sr-Ca- Cu-O systems; 2nd generation, Ba-R-Cu-O systems (R=lanthanides and yttrium); and 3rd generation, MgB2 systems. Our studies involved bulk materials, single crystals and thin films. This report gives a summary of our accomplishments, a list of publications, and 15 selected journal publications.

  16. The free energy of Maxwell-Vlasov equilibria

    International Nuclear Information System (INIS)

    Morrison, P.J.; Pfirsch, D.

    1989-10-01

    A previously derived expression for the energy of arbitrary perturbations about arbitrary Vlasov-Maxwell equilibria is transformed into a very compact form. The new form is also obtained by a canonical transformation method for solving Vlasov's equation, which is based on Lie group theory. This method is simpler than the one used before and provides better physical insight. Finally a procedure is presented for determining the existence of negative-energy modes. In this context the question of why there is an accessibility constraint for the particles, but not for the fields, is discussed. 16 refs

  17. Looking for multiple equilibria when geography matters : German city growth and the WWII shock

    NARCIS (Netherlands)

    Bosker, Maarten; Brakman, Steven; Garretsen, Harry; Schramm, Marc

    Based on the methodology of Davis and Weinstein, we look for multiple equilibria in German city growth. Bytaking the bombing of Germany during WWII as an example of a large, temporary shock, we analyze whether German city growth is characterized by multiple equilibria. In doing so, we allow for

  18. Computational study of the influence of mirror parameters on FRC (field-reversed configuration) equilibria:

    International Nuclear Information System (INIS)

    Fuentes, N.O.; Sakanaka, P.H.

    1990-01-01

    Field-reversed configuration equilibria are studied by solving the Grad-Shafranov equation. A multiple coil system (main coil and end mirrors) is considered to simulate the coil geometry of CNEA device. First results are presented for computed two-dimensional FRC equilibria produced varying the mirror coil current with two different mirror lenghts. (Author)

  19. How hard is it to find extreme Nash equilibria in network congestion games?

    NARCIS (Netherlands)

    Gassner, E.; Hatzl, J.; Krumke, S.O.; Sperber, H.; Woeginger, G.J.; Papadimitriou, C.; Zhang, S.

    2008-01-01

    We study the complexity of finding extreme pure Nash equilibria in symmetric (unweighted) network congestion games. In our context best and worst equilibria are those with minimum respectively maximum makespan. On series-parallel graphs a worst Nash equilibrium can be found by a Greedy approach

  20. A Novel Technique that Enables Efficient Conduct of Simultaneous Isomerization and Fermentation (SIF) of Xylose

    Science.gov (United States)

    Rao, Kripa; Chelikani, Silpa; Relue, Patricia; Varanasi, Sasidhar

    Of the sugars recovered from lignocellulose, D-glucose can be readily converted into ethanol by baker's or brewer's yeast (Saccharomyces cerevisiae). However, xylose that is obtained by the hydrolysis of the hemicellulosic portion is not fermentable by the same species of yeasts. Xylose fermentation by native yeasts can be achieved via isomerization of xylose to its ketose isomer, xylulose. Isomerization with exogenous xylose isomerase (XI) occurs optimally at a pH of 7-8, whereas subsequent fermentation of xylulose to ethanol occurs at a pH of 4-5. We present a novel scheme for efficient isomerization of xylose to xylulose at conditions suitable for the fermentation by using an immobilized enzyme system capable of sustaining two different pH microenvironments in a single vessel. The proof-of-concept of the two-enzyme pellet is presented, showing conversion of xylose to xylulose even when the immobilized enzyme pellets are suspended in a bulk solution whose pH is sub-optimal for XI activity. The co-immobilized enzyme pellets may prove extremely valuable in effectively conducting "simultaneous isomerization and fermentation" (SIF) of xylose. To help further shift the equilibrium in favor of xylulose formation, sodium tetraborate (borax) was added to the isomerization solution. Binding of tetrahydroxyborate ions to xylulose effectively reduces the concentration of xylulose and leads to increased xylose isomerization. The formation of tetrahydroxyborate ions and the enhancement in xylulose production resulting from the complexation was studied at two different bulk pH values. The addition of 0.05 M borax to the isomerization solution containing our co-immobilized enzyme pellets resulted in xylose to xylulose conversion as high as 86% under pH conditions that are suboptimal for XI activity. These initial findings, which can be optimized for industrial conditions, have significant potential for increasing the yield of ethanol from xylose in an SIF approach.

  1. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water.

    Science.gov (United States)

    Moliner, Manuel; Román-Leshkov, Yuriy; Davis, Mark E

    2010-04-06

    The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containing a catalytic amount of Sn-Beta (150 Sn:glucose molar ratio) gives product yields of approximately 46% (wt/wt) glucose, 31% (wt/wt) fructose, and 9% (wt/wt) mannose after 30 min and 12 min of reaction at 383 K and 413 K, respectively. This reactivity is achieved also when a 45 wt% glucose solution is used. The properties of the large-pore zeolite greatly influence the reaction behavior because the reaction does not proceed with a medium-pore zeolite, and the isomerization activity is considerably lower when the metal centers are incorporated in ordered mesoporous silica (MCM-41). The Sn-Beta catalyst can be used for multiple cycles, and the reaction stops when the solid is removed, clearly indicating that the catalysis is occurring heterogeneously. Most importantly, the Sn-Beta catalyst is able to perform the isomerization reaction in highly acidic, aqueous environments with equivalent activity and product distribution as in media without added acid. This enables Sn-Beta to couple isomerizations with other acid-catalyzed reactions, including hydrolysis/isomerization or isomerization/dehydration reaction sequences [starch to fructose and glucose to 5-hydroxymethylfurfural (HMF) demonstrated here].

  2. High temperature interdiffusion and phase equilibria in U-Mo

    International Nuclear Information System (INIS)

    Lundberg, L.B.

    1988-01-01

    Experimental data for interdiffusion and phase equilibria in the U-Mo system have been obtained over the temperature range 1400 to 1525 K as a fallout from compatibility experiments in which UO 2 was decomposed by lithium in closed molybdenum capsules. Composition-position, x-ray diffraction and microstructural data from the interdiffusion zones indicate that the intermediate phase U 2 Mo is found in this temperature range, contrary to the currently accepted equilibrium U-Mo phase diagram. The U-Mo interdiffusion data are in good agreement with published values. Inclusion of the U 2 Mo phase in a theoretical correlation of interdiffusion and phase equilibria data using Darken's equation indicate that high temperature interdiffusion of uranium and molybdenum follows the usual thermodynamic rules. Significant changes in the value of the thermodynamic based Darken factor near the U 2 Mo phase boundary on the high uranium side are indicated from both the new and published interdiffusion data. 9 refs., 10 figs., 3 tabs

  3. Phase equilibria of the Mo-Al-Ho ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yitai; Chen, Xiaoxian; Liu, Hao [Guangxi Univ., Nanning (China). College of Materials Science and Engineering; Guangxi Univ., Nanning (China). Guangxi Key Laboratory of Processing for Non-ferrous Metal and Featured Materials; Zhan, Yongzhong [Guangxi Univ., Nanning (China). College of Materials Science and Engineering; Guangxi Univ., Nanning (China). Guangxi Key Laboratory of Processing for Non-ferrous Metal and Featured Materials; Guangxi Univ., Nanning (China). Center of Ecological Collaborative Innovation for Aluminum Industry

    2017-08-15

    Investigation into the reactions and phase equilibria of transition metal elements (i.e. Mo, Zr, Cr, V and Ti), Al and rare earths is academically and industrially important for the development of both refractory alloys and lightweight high-temperature materials. In this work, the equilibria of the Mo-Al-Ho ternary system at 773 K have been determined by using X-ray powder diffraction and scanning electron microscopy equipped with energy dispersive X-ray analysis. A new ternary phase Al{sub 4}Mo{sub 2}Ho has been found and the other ternary phase Al{sub 43}Mo{sub 4}Ho{sub 6} is observed. Ten binary phases in the Al-Mo and Al-Ho systems, including Al{sub 17}Mo{sub 4} rather than Al{sub 4}Mo, have been determined to exist at 773 K. The homogeneity ranges of AlMo{sub 3} and Al{sub 8}Mo{sub 3} phase are 7.5 at.% and 1 at.%, respectively. According to the phase-disappearing method, the maximum solubility of Al in Mo is about 16 at.%.

  4. Electronic structure and phase equilibria in ternary substitutional alloys

    International Nuclear Information System (INIS)

    Traiber, A.J.S.; Allen, S.M.; Waterstrat, R.M.

    1996-01-01

    A reliable, consistent scheme to study phase equilibria in ternary substitutional alloys based on the tight-binding approximation is presented. With electronic parameters from linear muffin-tin orbital calculations, the computed density of states and band structures compare well with those from more accurate abinitio calculations. Disordered alloys are studied within the tight-binding coherent-potential approximation extended to alloys; energetics of ordered systems are obtained through effective pair interactions computed with the general perturbation method; and partially ordered alloys are studied with a novel simplification of the molecular coherent-potential approximation combined with the general perturbation method. The formalism is applied to bcc-based Zr-Ru-Pd alloys which are promising candidates for medical implant devices. Using energetics obtained from the above scheme, we apply the cluster- variation method to study phase equilibria for particular pseudo- binary alloys and show that results are consistent with observed behavior of electronic specific heat coefficient with composition for Zr 0.5 (Ru, Pd) 0.5

  5. Kinetic description of linear theta-pinch equilibria

    International Nuclear Information System (INIS)

    Batchelor, D.B.; Davidson, R.C.

    1975-01-01

    Equilibrium properties of linear theta-pinch plasmas are studied within the framework of the steady-state (o/x=0) Vlasov-Maxwell equations. The analysis is carried out for an infinitely long plasma column aligned parallel to an externally applied axial magnetic field Bsub(z)sup(ext)esub(z). Equilibrium properties are calculated for the class of rigid-rotor Vlasov equilibria, in which the th component distribution function (Hsub(perpendicular), Psub(theta), upsilonsub(z) depends on perpendicular energy H and canonical angular momentum Psub(theta), exclusively through the linear combination Hsub(perpendicular)-ωsub(j)Psub(theta), where ω;=const.=angular velocity of mean rotation. General equilibrium relations that pertain to the entire class of rigid-rotor Vlasov equilibria are discussed; and specific examples of sharp- and diffuse-boundary equilibrium configurations are considered. Rigid-rotor density and magnetic field profiles are compared with experimentally observed profiles. A general prescription is given for determining the functional dependence of the equilibrium distribution function on Hsub(perpendicular)-ωsub(j)Psub(theta) in circumstances, where the density profile or magnetic field profile is specified. (author)

  6. Phase equilibria in the niobium-vanadium-hydrogen system

    Energy Technology Data Exchange (ETDEWEB)

    Bethin, J. (Grumman Aerospace Corp., Bethpage, NY (USA)); Welch, D.O. (Brookhaven National Lab., Upton, NY (USA)); Pick, M.A. (Commission of the European Communities, Abingdon (UK). JET Joint Undertaking)

    1990-01-01

    The effect of vanadium additions to niobium on the metal-hydrogen phase equilibria has been studied. Measurements of the equilibrium H{sub 2}(D{sub 2}) pressure-composition-temperature isotherms for Nb{sub 1-x}V{sub x} alloys with 0{le}x<0.2 were used to determine the depression of the {alpha} - {alpha}' critical temperature with increasing vanadium concentration. A simple lattice-fluid model guided reduction of the data. Changes in the triple point temperature as well as the shift of the {zeta} {yields} {epsilon} phase transition were determined by differential scanning calorimetry measurements. A rapid overall depression was found, of the order of 7 K (at.% substituted V){sup -1}, for the metal-hydrogen (deuterium) phase boundary structure when compared with the Nb-H system in the hydrogen concentration range of interest. The results explain the enhanced terminal solubility of hydrogen in this system found previously by other authors. The changes in the phase equilibria are discussed in terms of the effect of hydrogen trapping and compared with the results of a cluster-variation calculation for random-field systems of previous authors, taking into account a distribution of H-site energies due to alloying. (author).

  7. Social Interactions under Incomplete Information: Games, Equilibria, and Expectations

    Science.gov (United States)

    Yang, Chao

    My dissertation research investigates interactions of agents' behaviors through social networks when some information is not shared publicly, focusing on solutions to a series of challenging problems in empirical research, including heterogeneous expectations and multiple equilibria. The first chapter, "Social Interactions under Incomplete Information with Heterogeneous Expectations", extends the current literature in social interactions by devising econometric models and estimation tools with private information in not only the idiosyncratic shocks but also some exogenous covariates. For example, when analyzing peer effects in class performances, it was previously assumed that all control variables, including individual IQ and SAT scores, are known to the whole class, which is unrealistic. This chapter allows such exogenous variables to be private information and models agents' behaviors as outcomes of a Bayesian Nash Equilibrium in an incomplete information game. The distribution of equilibrium outcomes can be described by the equilibrium conditional expectations, which is unique when the parameters are within a reasonable range according to the contraction mapping theorem in function spaces. The equilibrium conditional expectations are heterogeneous in both exogenous characteristics and the private information, which makes estimation in this model more demanding than in previous ones. This problem is solved in a computationally efficient way by combining the quadrature method and the nested fixed point maximum likelihood estimation. In Monte Carlo experiments, if some exogenous characteristics are private information and the model is estimated under the mis-specified hypothesis that they are known to the public, estimates will be biased. Applying this model to municipal public spending in North Carolina, significant negative correlations between contiguous municipalities are found, showing free-riding effects. The Second chapter "A Tobit Model with Social

  8. Thermal isomerization of regiospecifically 10B-labeled icosahedral carboranes

    International Nuclear Information System (INIS)

    Edvenson, G.M.; Gaines, D.F.

    1990-01-01

    Thermal treatment of regiospecifically 10 B-enriched (96%) 3-( 10 B)-1,2-C 2 n B 9 H 12 and 2-( 10 B)-1,7-C 2 n B 9 H 12 ( n B = boron with normal isotopic abundances) followed by 10 B and 11 B NMR analysis reveal that (1) 3-( 10 B)-1,2-C 2 n B 9 H 12 undergoes rearrangements that completely scramble the enriched boron atom, (2) these rearrangements occur at a rate faster than the conversion of 1,2-C 2 B 10 H 12 to 1,7-C 2 B 10 H 12 , (3) the 1,7-C 2 B 10 H 12 that is formed does not re-form 1,2-C 2 B 10 H 12 at a detectable rate, and (4) at temperatures at which 1,2-C 2 B 10 H 12 forms 1,7-C 2 B 10 H 12 at a significant rate, the latter undergoes no further rearrangements. The movement of 10 B at 350 degree C in 1,2-C 2 B 10 H 12 is compared to the movement predicted by various isomerization mechanisms. The mechanism that appears to give the closest agreement involves a 12-vertex nido intermediate. It was found that a number of previously considered mechanisms, including simple exchange between two boron sites, triangular face rotation in an icosahedron, diamond-square-diamond twist, and rotation of pentagonal pyramids, are extensions of the nido intermediate mechanism. The synthesis and thermal rearrangement of 3-F-3-( 10 B)-1,2-C 2 n B 9 H 11 demonstrate that independent intramolecular fluorine migration does not occur during rearrangement. 27 refs., 7 figs

  9. The development of isomerization catalysts for production of high-octane products

    Energy Technology Data Exchange (ETDEWEB)

    Pedrosa, A.M. Garrido; Melo, D.M.A.; Araujo, A.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Quimica; Souza, M.J.B.; Silva, A.O.S. [Universidade Federal do Rio Grande do Norte, Natal, RN (Brazil). Dept. de Engenharia Quimica

    2004-07-01

    In current petroleum industry, paraffins larger than C5 are used for catalytic reform. The catalytic reform is one of the most important processes for petroleum refine in reason of all reactions they drive to production of high-octane products. Reformate has high-octane products, but they contain 60% aromatics. Isomerization of C5- C7 can improve the octane number. The octane number of n-heptane is zero and increases after isomerization. For tri branched C7, the octane number reaches 113, which is higher than that of benzene. So, isomerization of C5-C7 is suggested to be a reasonable way to replace or partly replace the catalytic reforming process. It can decrease aromatics content with enhancement of octane number. Liquid acid catalysts were widely used in chemical industry in past decades. However, they face strong environmental challenges. The heavy corrosion of the reactor system is one of the main problems. Thus, solid acid catalysts are investigated for the isomerization reactions. The aim of this work is to develop a catalysts for the production of reformate products. Isomerization is catalyzed by metal-acid bifunctional catalysts. The metal components aid in hydrogenation, while the support, such as, zirconium, clays or zeolites, is the acidic component. (author)

  10. Dehydrogenation and concurrent isomerization of n-butenes on mixed tin and antimony oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Irvine, E.A.; Taylor, D.

    1978-01-01

    The dehydrogenation and concurrent isomerization of n-butenes on mixed tin and antimony oxide catalysts which had been outgassed at 698/sup 0/K were carried out in the presence of oxygen at 474/sup 0/K, and the initial approximately zero-order rates of 1,3-butadiene formation and rates of isomerization were used as a measure of catalytic activity to construct activity patterns as a function of catalyst composition. A comparison of the patterns with those for the isomerization of 3,3-dimethyl-1-butene and for the selective oxidation of propane on the same catalysts indicated that the dehydrogenation of 1-butene involves a m-allyl intermediate, but isomerization occurs through carbonium ion formation. For the cis- and trans-isomers, both reactions apparently occurred via a common allyl (but not m-allyl) intermediate. Dehydrogenation to butadiene decreased in the order 1-butene > cis-2-butene trans-2-butene and was maximum at 10% antimony for 1-butene and 21% antimony for 2-butene. Isomerization was always slower than dehydrogenation and showed two maEima, at 21 (or 27%) and at 75% antimony.

  11. Cryo-EM structure of isomeric molluscan hemocyanin triggered by viral infection.

    Directory of Open Access Journals (Sweden)

    Hongtao Zhu

    Full Text Available Hemocyanins (Hcs of arthropods and mollusks function not only as oxygen transporters, but also as phenoloxidases (POs. In invertebrates, PO is an important component in the innate immune cascade, where it functions as the initiator of melanin synthesis, a pigment involved in encapsulating and killing of pathogenic microbes. Although structures of Hc from several species of invertebrates have been reported, the structural basis for how PO activity is triggered by structural changes of Hc in vivo remains poorly understood. Here, we report a 6.8 Å cryo-electron microscopy (cryo-EM structure of the isomeric form of hemocyanin, which was isolated from Abalone Shriveling syndrome-associated Virus (AbSV infected abalone (Halitotis diversicolor, and build a pseudoatomic model of isomeric H. diversicolor hemocyanin 1 (HdH1. Our results show that, compared with native form of HdH1, the architecture of isomeric HdH1 turns into a more relaxed form. The interactions between certain functional units (FUs present in the native form of Hc either decreased or were totally abolished in the isomeric form of Hc. As a result of that, native state Hc switches to its isomeric form, enabling it to play its role in innate immune responses against invading pathogens.

  12. The Spectral Web of stationary plasma equilibria. II. Internal modes

    Science.gov (United States)

    Goedbloed, J. P.

    2018-03-01

    The new method of the Spectral Web to calculate the spectrum of waves and instabilities of plasma equilibria with sizeable flows, developed in the preceding Paper I [Goedbloed, Phys. Plasmas 25, 032109 (2018)], is applied to a collection of classical magnetohydrodynamic instabilities operating in cylindrical plasmas with shear flow or rotation. After a review of the basic concepts of the complementary energy giving the solution path and the conjugate path, which together constitute the Spectral Web, the cylindrical model is presented and the spectral equations are derived. The first example concerns the internal kink instabilities of a cylindrical force-free magnetic field of constant α subjected to a parabolic shear flow profile. The old stability diagram and the associated growth rate calculations for static equilibria are replaced by a new intricate stability diagram and associated complex growth rates for the stationary model. The power of the Spectral Web method is demonstrated by showing that the two associated paths in the complex ω-plane nearly automatically guide to the new class of global Alfvén instabilities of the force-free configuration that would have been very hard to predict by other methods. The second example concerns the Rayleigh-Taylor instability of a rotating theta-pinch. The old literature is revisited and shown to suffer from inconsistencies that are remedied. The most global n = 1 instability and a cluster sequence of more local but much more unstable n =2 ,3 ,…∞ modes are located on separate solution paths in the hydrodynamic (HD) version of the instability, whereas they merge in the MHD version. The Spectral Web offers visual demonstration of the central position the HD flow continuum and of the MHD Alfvén and slow magneto-sonic continua in the respective spectra by connecting the discrete modes in the complex plane by physically meaningful curves towards the continua. The third example concerns the magneto-rotational instability

  13. Hermite Polynomials and the Inverse Problem for Collisionless Equilibria

    Science.gov (United States)

    Allanson, O.; Neukirch, T.; Troscheit, S.; Wilson, F.

    2017-12-01

    It is long established that Hermite polynomial expansions in either velocity or momentum space can elegantly encode the non-Maxwellian velocity-space structure of a collisionless plasma distribution function (DF). In particular, Hermite polynomials in the canonical momenta naturally arise in the consideration of the 'inverse problem in collisionless equilibria' (IPCE): "for a given macroscopic/fluid equilibrium, what are the self-consistent Vlasov-Maxwell equilibrium DFs?". This question is of particular interest for the equilibrium and stability properties of a given macroscopic configuration, e.g. a current sheet. It can be relatively straightforward to construct a formal solution to IPCE by a Hermite expansion method, but several important questions remain regarding the use of this method. We present recent work that considers the necessary conditions of non-negativity, convergence, and the existence of all moments of an equilibrium DF solution found for IPCE. We also establish meaningful analogies between the equations that link the microscopic and macrosopic descriptions of the Vlasov-Maxwell equilibrium, and those that solve the initial value problem for the heat equation. In the language of the heat equation, IPCE poses the pressure tensor as the 'present' heat distribution over an infinite domain, and the non-Maxwellian features of the DF as the 'past' distribution. We find sufficient conditions for the convergence of the Hermite series representation of the DF, and prove that the non-negativity of the DF can be dependent on the magnetisation of the plasma. For DFs that decay at least as quickly as exp(-v^2/4), we show non-negativity is guaranteed for at least a finite range of magnetisation values, as parameterised by the ratio of the Larmor radius to the gradient length scale. 1. O. Allanson, T. Neukirch, S. Troscheit & F. Wilson: From one-dimensional fields to Vlasov equilibria: theory and application of Hermite polynomials, Journal of Plasma Physics, 82

  14. High spin states and isomeric decays in doubly-odd 208Fr

    International Nuclear Information System (INIS)

    Kanjilal, D.; Bhattacharya, S.; Goswami, A.; Kshetri, R.; Raut, R.; Saha, S.; Bhowmik, R.K.; Gehlot, J.; Muralithar, S.; Singh, R.P.; Jnaneswari, G.; Mukherjee, G.; Mukherjee, B.

    2010-01-01

    Neutron deficient isotopes of francium (Z=87, N∼121-123) as excited nuclei were produced in the fusion-evaporation reaction: 197 Au( 16 O, xn) 213-x Fr at 100 MeV. The γ rays from the residues were observed through the high sensitivity Germanium Clover detector array INGA. The decay of the high spin states and the isomeric states of the doubly-odd 208 Fr nuclei, identified from the known sequence of ground state transitions, were observed. The half-lives of the E γ =194(2) keV isomeric transition, known from earlier observations, was measured to be T 1/2 =233(18) ns. A second isomeric transition at E γ =383(2) keV and T 1/2 =33(7) ns was also found. The measured half-lives were compared with the corresponding single particle estimates, based on the level scheme obtained from the experiment.

  15. Structural and spectral comparisons between isomeric benzisothiazole and benzothiazole based aromatic heterocyclic dyes

    Science.gov (United States)

    Wang, Yin-Ge; Wang, Yue-Hua; Tao, Tao; Qian, Hui-Fen; Huang, Wei

    2015-09-01

    A pair of isomeric heterocyclic compounds, namely 3-amino-5-nitro-[2,1]-benzisothiazole and 2-amino-6-nitrobenzothiazole, are used as the diazonium components to couple with two N-substituted 4-aminobenzene derivatives. As a result, two pairs of isomeric aromatic heterocyclic azo dyes have been produced and they are structurally and spectrally characterized and compared including single-crystal structures, electronic spectra, solvatochromism and reversible acid-base discoloration, thermal stability and theoretically calculations. It is concluded that both benzisothiazole and benzothiazole based dyes show planar molecular structures and offset π-π stacking interactions, solvatochromism and reversible acid-base discoloration. Furthermore, benzisothiazole based aromatic heterocyclic dyes exhibit higher thermal stability, larger solvatochromic effects and maximum absorption wavelengths than corresponding benzothiazole based ones, which can be explained successfully by the differences of their calculated isomerization energy, dipole moment and molecular band gaps.

  16. Special features of isomeric ratios in nuclear reactions induced by various projectile particles

    Energy Technology Data Exchange (ETDEWEB)

    Danagulyan, A. S.; Hovhannisyan, G. H., E-mail: hov-gohar@ysu.am; Bakhshiyan, T. M.; Martirosyan, G. V. [Yerevan State University (Armenia)

    2016-05-15

    Calculations for (p, n) and (α, p3n) reactions were performed with the aid of the TALYS-1.4 code. Reactions in which the mass numbers of target and product nuclei were identical were examined in the range of A = 44–124. Excitation functions were obtained for product nuclei in ground and isomeric states, and isomeric ratios were calculated. The calculated data reflect well the dependence of the isomeric ratios on the projectile type. A comparison of the calculated and experimental data reveals, that, for some nuclei in a high-spin state, the calculated data fall greatly short of their experimental counterparts. These discrepancies may be due to the presence of high-spin yrast states and rotational bands in these nuclei. Calculations involving various level-density models included in the TALYS-1.4 code with allowance for the enhancement of collective effects do not remove the discrepancies in the majority of cases.

  17. Possible evidence for shape isomeric γ-decay in μ- atoms of 238U

    International Nuclear Information System (INIS)

    Fromm, W.D.; Ortlepp, H.-G.; Polikanov, S.M.; Schmidt, U.; Zorin, G.N.; Arlt, R.; Musiol, G.

    1977-01-01

    A search for the γ-decay of the shape isomer in muonic 238 U excited by radiationless transitions has been performed. Seven delayed transitions in the energy region of 700 to 3200 keV have been observed with a large Ge(Li) detector. Two transitions with Esub(γ)=2215 and 3131 keV have been attributed to the decay of the shape isomeric state into levels in the first well. The isomeric shift of the second minimum Esub(II) approximately 600 keV in the presence of the muon and the decrease of the lifetime of the shape isomer to tau=12+-2 ns give arguments in favour of the connection of shape isomerism with large quadrupole deformations. (Auth.)

  18. High-spin μs isomeric states in 96 Ag

    International Nuclear Information System (INIS)

    Becerril, A. D.; Lorusso, G.; Amthor, A. M.; Brown, B. A.; Estrade, A.; Guess, C. J.; Hitt, G. W.; Meharchand, R.; Schatz, H.; Smith, K.; Zegers, R. G. T.; Baumann, T.; Bazin, D.; Ginter, T.; Hausmann, M.; Minamisono, K.; Portillo, M.; Stolz, A.; Berryman, J. S.; Crawford, H. L.

    2011-01-01

    The isomeric and β decays of the N=Z+2 nucleus 96 Ag were investigated at the National Superconducting Cyclotron Laboratory. A cascade of γ-ray transitions originating from the deexcitation of a microsecond isomer was observed for the first time and was found in coincidence with two previously known transitions with energies of 470 and 667 keV. The isomeric half-life was determined as 1.45(7) μs, more precise than previously reported. The existence of a second, longer-lived microsecond isomer, associated with a 743-keV γ transition, is also proposed here. Shell model results within the (p 3/2 p 1/2 f 5/2 g 9/2 ) model space, using the jj44b interaction, reproduced level energies and isomeric decay half-lives reasonably well.

  19. Synthesis, structure and isomerism of three-bridge exo-nido-osmacarborane clusters

    International Nuclear Information System (INIS)

    Kolomnikova, G.D.; Petrovskij, P.V.; Sorokin, P.V.; Dolgushin, F.M.; Yanovskij, A.I.; Chizhevskij, I.T.

    2001-01-01

    The structure and isomerism of exo-nido-osmacarboranes prepared by reaction between coordination-unsaturated complex OsCl 2 (PPh 3 ) 3 (Ph-phenyl) in benzene at 20 deg C and K + -salts of nido-dicarbaundecarborate anions were studied by the methods of 1 H and 11 B NMR (including usual and two-dimensional spectra) and X-ray diffraction analysis. It was ascertained that in the compounds prepared osmium-containing group is bound with nido-carborane ligand via three-center bonds, open pentagonal plane of carborane ligand being retained in the isomers. In it nature isomerism in the compounds mentioned is geometrical cis-trans-isomerism [ru

  20. Glucose isomerization in simulated moving bed reactor by Glucose isomerase

    Directory of Open Access Journals (Sweden)

    Eduardo Alberto Borges da Silva

    2006-05-01

    Full Text Available Studies were carried out on the production of high-fructose syrup by Simulated Moving Bed (SMB technology. A mathematical model and numerical methodology were used to predict the behavior and performance of the simulated moving bed reactors and to verify some important aspects for application of this technology in the isomerization process. The developed algorithm used the strategy that considered equivalences between simulated moving bed reactors and true moving bed reactors. The kinetic parameters of the enzymatic reaction were obtained experimentally using discontinuous reactors by the Lineweaver-Burk technique. Mass transfer effects in the reaction conversion using the immobilized enzyme glucose isomerase were investigated. In the SMB reactive system, the operational variable flow rate of feed stream was evaluated to determine its influence on system performance. Results showed that there were some flow rate values at which greater purities could be obtained.Neste trabalho a tecnologia de Leito Móvel Simulado (LMS reativo é aplicada no processo de isomerização da glicose visando à produção de xarope concentrado de frutose. É apresentada a modelagem matemática e uma metodologia numérica para predizer o comportamento e o desempenho de unidades reativas de leito móvel simulado para verificar alguns aspectos importantes para o emprego desta tecnologia no processo de isomerização. O algoritmo desenvolvido utiliza a abordagem que considera as equivalências entre as unidades reativas de leito móvel simulado e leito móvel verdadeiro. Parâmetros cinéticos da reação enzimática são obtidos experimentalmente usando reatores em batelada pela técnica Lineweaver-Burk. Efeitos da transferência de massa na conversão de reação usando a enzima imobilizada glicose isomerase são verificados. No sistema reativo de LMS, a variável operacional vazão da corrente de alimentação é avaliada para conhecer o efeito de sua influência no

  1. Impacts of daily intakes on the isomeric profiles of perfluoroalkyl substances (PFASs) in human serum.

    Science.gov (United States)

    Shan, Guoqiang; Wang, Zhi; Zhou, Lianqiu; Du, Pin; Luo, Xiaoxiao; Wu, Qiannian; Zhu, Lingyan

    2016-01-01

    Perfluoroalkyl substances (PFASs) have been well studied in human daily intake for assessment of potential health risks. However, little is known about the isomeric compositions of PFASs in daily intake and their impacts on isomeric profiles in humans. In this study, we investigated the occurrence of PFASs with isomeric analysis in various human exposure matrices including foodstuffs, tap water and indoor dust. Perfluorooctanesulfonate (PFOS) and/or perfluorooctanoate (PFOA) were predominant in these exposure matrices collected in Tianjin, China. In fish and meat, linear (n-) PFOA was enriched with a percentage of 92.2% and 99.6%, respectively. Although n-PFOS was higher in fish (84.8%) than in technical PFOS (ca. 70%), it was much lower in meat (63.1%) and vegetables (58.5%). Dietary intake contributed >99% of the estimated daily intake (EDI) for the general population. The isomeric profiles of PFOA and PFOS in human serum were predicted based on the EDI and a one-compartment, first-order pharmacokinetic model. The isomeric percentage of n-PFOA in the EDI (98.6%) was similar to that in human serum (predicted: 98.2%, previously measured: 99.7%) of Tianjin residents. The results suggest direct PFOA intake plays an important role in its isomeric compositions in humans. For PFOS, the predicted n-PFOS (69.3%) was much higher than the previously measured values (59.2%) in human serum. This implies that other factors, such as indirect exposure to PFOS precursors and multiple excretion pathways, may contribute to the lower percentage of n-PFOS in humans than of technical PFOS. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Recent developments in Bayesian inference of tokamak plasma equilibria and high-dimensional stochastic quadratures

    International Nuclear Information System (INIS)

    Von Nessi, G T; Hole, M J

    2014-01-01

    We present recent results and technical breakthroughs for the Bayesian inference of tokamak equilibria using force-balance as a prior constraint. Issues surrounding model parameter representation and posterior analysis are discussed and addressed. These points motivate the recent advancements embodied in the Bayesian Equilibrium Analysis and Simulation Tool (BEAST) software being presently utilized to study equilibria on the Mega-Ampere Spherical Tokamak (MAST) experiment in the UK (von Nessi et al 2012 J. Phys. A 46 185501). State-of-the-art results of using BEAST to study MAST equilibria are reviewed, with recent code advancements being systematically presented though out the manuscript. (paper)

  3. Oscillations and Multiple Equilibria in Microvascular Blood Flow.

    Science.gov (United States)

    Karst, Nathaniel J; Storey, Brian D; Geddes, John B

    2015-07-01

    We investigate the existence of oscillatory dynamics and multiple steady-state flow rates in a network with a simple topology and in vivo microvascular blood flow constitutive laws. Unlike many previous analytic studies, we employ the most biologically relevant models of the physical properties of whole blood. Through a combination of analytic and numeric techniques, we predict in a series of two-parameter bifurcation diagrams a range of dynamical behaviors, including multiple equilibria flow configurations, simple oscillations in volumetric flow rate, and multiple coexistent limit cycles at physically realizable parameters. We show that complexity in network topology is not necessary for complex behaviors to arise and that nonlinear rheology, in particular the plasma skimming effect, is sufficient to support oscillatory dynamics similar to those observed in vivo.

  4. Dynamic data evaluation for solid-liquid equilibria

    DEFF Research Database (Denmark)

    Cunico, Larissa; Ceriani, Roberta; Kang, Jeong Won

    The accuracy and reliability of the measured data sets to be used in regression of model parameters is an important issue related to modeling of phase equilibria. It is clear that good parameters for any model cannot be obtained from low quality data. A thermodynamic consistency test for solid...... and parameter regression. The paper will highlight the data collection, the data analysis for SLE data and the thermodynamic model performance (such as NRTL, UNIQUAC and original UNIFAC)....... studies considering the methodology proposed for SLE thermodynamic consistency tests and data from open literature and databases such as NIST-TDE®, DIPPR® and DECHEMA® are presented. The SLE consistency test and data evaluation is performed in a software containing option for data analysis, model analysis...

  5. Modified Poisson eigenfunctions for electrostatic Bernstein--Greene--Kruskal equilibria

    International Nuclear Information System (INIS)

    Ling, K.; Abraham-Shrauner, B.

    1981-01-01

    The stability of an electrostatic Bernstein--Greene--Kruskal equilibrium by Lewis and Symon's general linear stability analysis for spatially inhomogeneous Vlasov equilibria, which employs eigenfunctions and eigenvalues of the equilibrium Liouville operator and the modified Poisson operator, is considered. Analytic expressions for the Liouville eigenfuctions and eigenvalues have already been given; approximate analytic expressions for the dominant eigenfunction and eigenvalue of the modified Poisson operator are given. In the kinetic limit three methods are given: (i) the perturbation method, (ii) the Rayleigh--Ritz method, and (iii) a method based on a Hill's equation. In the fluid limit the Rayleigh--Ritz method is used. The dominant eigenfunction and eigenvalue are then substituted in the dispersion relation and the growth rate calculated. The growth rate agrees very well with previous results found by numerical simulation and by modified Poisson eigenfunctions calculated numerically

  6. Bifurcated equilibria in two-dimensional MHD with diamagnetic effects

    International Nuclear Information System (INIS)

    Ottaviani, M.; Tebaldi, C.

    1998-12-01

    In this work we analyzed the sequence of bifurcated equilibria in two-dimensional reduced magnetohydrodynamics. Diamagnetic effects are studied under the assumption of a constant equilibrium pressure gradient, not altered by the formation of the magnetic island. The formation of an island when the symmetric equilibrium becomes unstable is studied as a function of the tearing mode stability parameter Δ' and of the diamagnetic frequency, by employing fixed-points numerical techniques and an initial value code. At larger values of Δ' a tangent bifurcation takes place, above which no small island solutions exist. This bifurcation persists up to fairly large values of the diamagnetic frequency (of the order of one tenth of the Alfven frequency). The implications of this phenomenology for the intermittent MHD dynamics observed in tokamaks is discussed. (authors)

  7. Gas hydrate phase equilibria measurement techniques and phase rule considerations

    International Nuclear Information System (INIS)

    Beltran, Juan G.; Bruusgaard, Hallvard; Servio, Phillip

    2012-01-01

    Highlights: → Inconsistencies found in hydrate literature. → Clarification to the number of variables needed to satisfy and justify equilibrium data. → Application of phase rule to mixed hydrate systems. → Thermodynamically consistent format to present data. - Abstract: A brief review of the Gibbs phase rule for non-reacting systems and its correct application to clathrate hydrates is presented. Clarification is provided for a common mistake found in hydrate phase-equilibria literature, whereby initial compositions are used as intensive variables to satisfy the Gibbs phase rule instead of the equilibrium values. The system of (methane + carbon dioxide + water) under (hydrate + liquid + vapor) equilibrium is used as a case study to illustrate key points and suggestions to improve experimental techniques are proposed.

  8. High-pressure fluid phase equilibria phenomenology and computation

    CERN Document Server

    Deiters, Ulrich K

    2012-01-01

    The book begins with an overview of the phase diagrams of fluid mixtures (fluid = liquid, gas, or supercritical state), which can show an astonishing variety when elevated pressures are taken into account; phenomena like retrograde condensation (single and double) and azeotropy (normal and double) are discussed. It then gives an introduction into the relevant thermodynamic equations for fluid mixtures, including some that are rarely found in modern textbooks, and shows how they can they be used to compute phase diagrams and related properties. This chapter gives a consistent and axiomatic approach to fluid thermodynamics; it avoids using activity coefficients. Further chapters are dedicated to solid-fluid phase equilibria and global phase diagrams (systematic search for phase diagram classes). The appendix contains numerical algorithms needed for the computations. The book thus enables the reader to create or improve computer programs for the calculation of fluid phase diagrams. introduces phase diagram class...

  9. A new transiently chaotic flow with ellipsoid equilibria

    Science.gov (United States)

    Panahi, Shirin; Aram, Zainab; Jafari, Sajad; Pham, Viet-Thanh; Volos, Christos; Rajagopal, Karthikeyan

    2018-03-01

    In this article, a simple autonomous transiently chaotic flow with cubic nonlinearities is proposed. This system represents some unusual features such as having a surface of equilibria. We shall describe some dynamical properties and behaviours of this system in terms of eigenvalue structures, bifurcation diagrams, time series, and phase portraits. Various behaviours of this system such as periodic and transiently chaotic dynamics can be shown by setting special parameters in proper values. Our system belongs to a newly introduced category of transiently chaotic systems: systems with hidden attractors. Transiently chaotic behaviour of our proposed system has been implemented and tested by the OrCAD-PSpise software. We have found a proper qualitative similarity between circuit and simulation results.

  10. A fast, user-friendly code for calculating magnetohydrodynamic equilibria

    International Nuclear Information System (INIS)

    Haney, S.W.; Freidberg, J.P.; Solomon, C.J.

    1995-01-01

    Using variational techniques, we have developed a fast, user-friendly code for computing approximate, but highly accurate fixed boundary magnetohydrodynamic equilibria for tokamak plasmas. The variational procedure simplifies the problem---a two-dimensional nonlinear partial differential equation---to a set of nonlinear algebraic equations. The reduced problem can be readily solved on workstations or personal computers. This allows us to exploit sophisticated graphical user interfaces that make supplying calculation data and viewing results easy. This ease-of-use, along with the semianalytic nature of our calculation, allows researchers to routinely incorporate equilibrium information into their work. It also provides a tool for educators teaching fusion theory. We describe the variational formulation, the speed and accuracy of the computer implementation, and the design and operation of a user-friendly graphical interface

  11. NaSO2Ph Induced Exclusive Isomerization of 1,2-Allenyl Sulfoxides to 2-Alkynylic Phenyl Sulfoxides

    Institute of Scientific and Technical Information of China (English)

    傅春玲; 麻生明

    2005-01-01

    The clean isomerization of 1,2-allenyl sulfoxides in the presence of NaSO2Ph afforded 2-alkynylic phenyl sulfoxides in good yields and selectivities. Although strong base-catalyzed isomerization of allenes to alkynes is known, the mechanism for the current reaction is interesting for the obvious reason that NaSOEPh is a weak base.

  12. Metamorphism and partial melting of ordinary chondrites: Calculated phase equilibria

    Science.gov (United States)

    Johnson, T. E.; Benedix, G. K.; Bland, P. A.

    2016-01-01

    Constraining the metamorphic pressures (P) and temperatures (T) recorded by meteorites is key to understanding the size and thermal history of their asteroid parent bodies. New thermodynamic models calibrated to very low P for minerals and melt in terrestrial mantle peridotite permit quantitative investigation of high-T metamorphism in ordinary chondrites using phase equilibria modelling. Isochemical P-T phase diagrams based on the average composition of H, L and LL chondrite falls and contoured for the composition and abundance of olivine, ortho- and clinopyroxene, plagioclase and chromite provide a good match with values measured in so-called equilibrated (petrologic type 4-6) samples. Some compositional variables, in particular Al in orthopyroxene and Na in clinopyroxene, exhibit a strong pressure dependence when considered over a range of several kilobars, providing a means of recognising meteorites derived from the cores of asteroids with radii of several hundred kilometres, if such bodies existed at that time. At the low pressures (recorders of peak conditions. The intersection of isopleths of these variables may allow pressures to be quantified, even at low P, permitting constraints on the minimum size of parent asteroid bodies. The phase diagrams predict the onset of partial melting at 1050-1100 °C by incongruent reactions consuming plagioclase, clinopyroxene and orthopyroxene, whose compositions change abruptly as melting proceeds. These predictions match natural observations well and support the view that type 7 chondrites represent a suprasolidus continuation of the established petrologic types at the extremes of thermal metamorphism. The results suggest phase equilibria modelling has potential as a powerful quantitative tool in investigating, for example, progressive oxidation during metamorphism, the degree of melting and melt loss or accumulation required to produce the spectrum of differentiated meteorites, and whether the onion shell or rubble pile

  13. Self-consistent equilibria in cylindrical reversed-field pinch

    International Nuclear Information System (INIS)

    Lo Surdo, C.; Paccagnella, R.; Guo, S.

    1995-03-01

    The object of this work is to study the self-consistent magnetofluidstatic equilibria of a 2-region (plasma + gas) reversed-field pinch (RFP) in cylindrical approximation (namely, with vanishing inverse aspect ratio). Differently from what happens in a tokamak, in a RFP a significant part of the plasma current is driven by a dynamo electric field (DEF), in its turn mainly due to plasma turbulence. So, it is worked out a reasonable mathematical model of the above self-consistent equilibria under the following main points it has been: a) to the lowest order, and according to a standard ansatz, the turbulent DEF say ε t , is expressed as a homogeneous transform of the magnetic field B of degree 1, ε t =(α) (B), with α≡a given 2-nd rank tensor, homogeneous of degree 0 in B and generally depending on the plasma state; b) ε t does not explicitly appear in the plasma energy balance, as it were produced by a Maxwell demon able of extract the corresponding Joule power from the plasma. In particular, it is showed that, if both α and the resistivity tensor η are isotropic and constant, the magnetic field is force-free with abnormality equal to αη 0 /η, in the limit of vanishing β; that is, the well-known J.B. Taylor'result is recovered, in this particular conditions, starting from ideas quite different from the usual ones (minimization of total magnetic energy under constrained total elicity). Finally, the general problem is solved numerically under circular (besides cylindrical) symmetry, for simplicity neglecting the existence of gas region (i.e., assuming the plasma in direct contact with the external wall)

  14. Phase equilibria and molecular interaction studies on (naphthols + vanillin) systems

    International Nuclear Information System (INIS)

    Gupta, Preeti; Agrawal, Tanvi; Das, Shiva Saran; Singh, Nakshatra Bahadur

    2012-01-01

    Highlights: ► Phase equilibria of (naphthol + vanillin) systems have been studied for the first time. ► Eutectic type phase diagrams are obtained. ► Eutectic mixtures show nonideal behaviour. ► There is a weak molecular interaction between the components in the eutectic mixtures. ► α-Naphthol–vanillin eutectic is more stable as compared to β-naphthol–vanillin. - Abstract: Phase equilibria between (α-naphthol + vanillin) and (β-naphthol + vanillin) systems have been studied by thaw-melt method and the results show the formation of simple eutectic mixtures. Crystallization velocities of components and eutectic mixtures were determined at different stages under cooling. With the help of differential scanning calorimeter (DSC), the enthalpy of fusion of components and eutectic mixtures was determined and from the values excess thermodynamic functions viz., excess Gibbs free energy (G E ), excess entropy (S E ), excess enthalpy (H E ) of hypo-, hyper- and eutectic mixtures were calculated. Flexural strength measurements were made in order to understand the non-ideal nature of eutectics. FT-IR spectral studies indicate the formation of hydrogen bond in the eutectic mixture. Anisotropic and isotropic microstructural studies of components, hypo-, hyper- and eutectic mixtures were made. Jackson’s roughness parameter was calculated and found to be greater than 2 suggesting the faceted morphology with irregular structures. The overall results have shown that there is a weak molecular interaction between the components in the eutectic mixtures and the (α-naphthol + vanillin) eutectic is more stable as compared to the (β-naphthol + vanillin) eutectic system.

  15. Consequences of acid strength for isomerization and elimination catalysis on solid acids.

    Science.gov (United States)

    Macht, Josef; Carr, Robert T; Iglesia, Enrique

    2009-05-13

    We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic

  16. Excitation of isomeric states 1h11/2 in (γ, n) reactions

    International Nuclear Information System (INIS)

    Tonchev, A.P.; Gangrskij, Yu.P.; Belov, A.G.

    1995-01-01

    The cross sections of (γ, n) reactions were measured for ground and isomeric states 1h 11/2 in 16 isotopes of Pd, Cd, Sn, Te, Ba, Ce, Nd and Sm. The energy of γ-rays was placed in the region of Giant Dipole Resonance. An activation method of measurements has been used. IR dependence of neutron and proton number in nucleus was detected and of excitation energy of residual nucleus as well. Different factors influencing the values of the isomeric ratios are discussed. 20 refs., 5 figs., 2 tabs

  17. Isomeric ratio measurements for the radiative neutron capture 176Lu(n,γ at DANCE

    Directory of Open Access Journals (Sweden)

    Denis-Petit D.

    2017-01-01

    Full Text Available The isomeric ratios for the neutron capture reaction 176Lu(n,γ to the Jπ = 5/2−, 761.7 keV, T1/2 = 32.8 ns and the Jπ = 15/2+, 1356.9 keV, T1/2 = 11.1 ns levels of 177Lu, have been measured for the first time with the Detector for Advanced Neutron Capture Experiments (DANCE at the Los Alamos National Laboratory. These measured isomeric ratios are compared with TALYS calculations.

  18. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water

    OpenAIRE

    Moliner, Manuel; Román-Leshkov, Yuriy; Davis, Mark E.

    2010-01-01

    The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup (HFCS; reaction performed by enzyme catalysts) and recently is being considered as an intermediate step in the possible route of biomass to fuels and chemicals. Here, it is shown that a large-pore zeolite that contains tin (Sn-Beta) is able to isomerize glucose to fructose in aqueous media with high activity and selectivity. Specifically, a 10% (wt/wt) glucose solution containin...

  19. Kinetic and mass transfer studies on the isomerization of cellulose hydrolyzate using immobilized Streptomyces cells

    Energy Technology Data Exchange (ETDEWEB)

    Ghose, T K; Chand, S

    1978-01-01

    Streptomyces cells possessing glucose isomerase activity, heat-treated and confined within polyester sacs have been used in batch/continuous isomerization of enzymatically hydrolyzed microcrystalline cellulose. Conversion data at different concentrations of substrate closely follow the reactor performance equation based on the reaction kinetics. The effect of external film and pore diffusional resistances were experimentally found to be negligible. The dispersion effects in the packed bed column have been evaluated by pulse input tracer analysis. Continuous operation of the column to isomerize cellulose hydrolyzate (2.0 M glucose) showed an exponential deactivation of enzyme activity with a half-life of 447 h.

  20. Efficient Isomerization of Glucose to Fructose over Zeolites in Consecutive Reactions in Alcohol and Aqueous Media

    DEFF Research Database (Denmark)

    Shunmugavel, Saravanamurugan; Paniagua, Marta; Melero, Juan A

    2013-01-01

    glucose isomerization to fructose and subsequent reaction with methanol to form methyl fructoside (step 1), followed by hydrolysis to re-form fructose after water addition (step 2). NMR analysis with (13)C-labeled sugars confirmed this reaction pathway. Conversion of glucose for 1 h at 120 °C with H......-USY (Si/Al = 6) gave a remarkable 55% yield of fructose after the second reaction step. A main advantage of applying alcohol media and a catalyst that combines Brønsted and Lewis acid sites is that glucose is isomerized to fructose at low temperatures, while direct conversion to industrially important...

  1. High-pressure liquid chromatographic determination of chlorphenesin carbamate and the beta-isomeric carbamate.

    Science.gov (United States)

    Beyer, W F

    1976-12-01

    A high-pressure liquid chromatographic assay was developed for the determination of chlorphenesin carbamate and its beta-isomeric carbamate. A single 4-mm i.d. X 30-cm column, prepacked with 10 micrometer fully porous silica gel particles, is used with 3% methanol in 50% water-saturated butyl chloride as the mobile phase. The procedure separates chlorphenesin carbamate from several possible impurities in addition to the beta-isomeric carbamate. The assay was applied to bulk drug and compressed tablets. The relative standard deviations for the assays of chlorphenesin carbamate and the beta-isomer are approximately 1 and 2%, respectively.

  2. Preparing isomerically pure beams of short-lived nuclei at JYFLTRAP

    Energy Technology Data Exchange (ETDEWEB)

    Eronen, T. [Department of Physics, University of Jyvaeskylae, P.O. Box 35 (YFL), FIN-40014 (Finland)], E-mail: tommi.eronen@jyu.fi; Elomaa, V.-V.; Hager, U.; Hakala, J.; Jokinen, A.; Kankainen, A.; Rahaman, S.; Rissanen, J.; Weber, C.; Aystoe, J. [Department of Physics, University of Jyvaeskylae, P.O. Box 35 (YFL), FIN-40014 (Finland)

    2008-10-15

    A new procedure to prepare isomerically clean samples of short-lived ions with a mass resolving power of more than 1 x 10{sup 5} has been developed at the JYFLTRAP tandem Penning trap system. The method utilises a dipolar rf-excitation of the ion motion with separated oscillatory fields in the precision trap. During a subsequent retransfer to the purification trap, the contaminants are rejected and as a consequence, the remaining bunch is isomerically cleaned. This newly-developed method is suitable for very high-resolution cleaning and is at least a factor of five faster than the methods used so far in Penning trap mass spectrometry.

  3. Determination of the active site and mechanism for alkene isomerization in Cu(II) exchnaged Y-type zeolite

    Energy Technology Data Exchange (ETDEWEB)

    John, C S; Leach, H F

    1977-01-01

    An ESR study of 1-butene isomerization at 315/sup 0/-375/sup 0/C, 3,3-dimethyl-1-butene isomerization to 2,3-dimethyl-1- and -2-butene at 293/sup 0/K, and deuterium redistribution in 3,3-dideuteriopropene at 363/sup 0/-396/sup 0/K showed the presence of two copper(II) species in different environments, which reacted with the olefins at different rates. Although activation energies for the three reactions differed and only dideuteriopropene showed an induction period, a similar mechanism is proposed in all cases, involving preliminary reduction of copper(II), with the rates of reduction and isomerization differing from olefin to olefin. Apparently, the active site for the isomerization is a Broensted acid generated by the reduction, and the isomerization follows an associative (proton addition-elimination) mechanism with a carbonium ion intermediate. Spectra, graphs, diagram, and 12 references.

  4. A Multistep Equilibria-Redox-Complexation Demonstration to Illustrate Le Chatelier's Principle.

    Science.gov (United States)

    Berger, Tomas G.; Mellon, Edward K.

    1996-01-01

    Describes a process that can be used to illustrate a number of chemical principles including Le Chatelier's principle, redox chemistry, equilibria versus steady state situations, and solubility of species. (JRH)

  5. Thermodynamics and phase equilibria of ternary systems relevant to contact materials for compound semiconductors

    International Nuclear Information System (INIS)

    Ipser, H.; Richter, K.; Micke, K.

    1997-01-01

    In order to investigate the stability of ohmic contacts to compound semiconductors, it is necessary to know the phase equilibria in the corresponding multi-component systems. We are currently studying the phase equilibria and thermophysical properties of several ternary systems which are of interest in view of the use of nickel, palladium and platinum as contact materials for GaSb and InSb compound semiconductors: Ga-Ni-Sb, In-Ni-Sb, Ga-Pd-Sb and Ga-Pt-Sb. Phase equilibria are investigated by thermal analyses, X-ray powder diffraction methods as well as electron microprobe analysis. Thermodynamic properties are derived from vapour pressure measurements using an isopiestic method. It is planned to combine all information on phase equilibria and thermochemistry for the ternary and the limiting binary systems to perform an optimization of the ternary systems by computer calculations using standard software. (author)

  6. Kinetic stability constraints on magnetized plasma equilibria: Quasi-particle approach

    International Nuclear Information System (INIS)

    Sosenko, P.; Weiland, J.

    1996-01-01

    Macroscopic adiabatic invariants for the magnetized plasma are studied within the context of the quasi-particle description, as well as constraints which they impose on energy transfer and stable plasma equilibria. 6 refs

  7. Anticonvulsant effects of isomeric nonimidazole histamine H3 receptor antagonists

    Directory of Open Access Journals (Sweden)

    Sadek B

    2016-11-01

    , in which 3-piperidinopropan-1-ol in ligand 2 was replaced by (4-(3-(piperidin-1-ylpropoxyphenylmethanol, and its (S-enantiomer (4 significantly and in a dose-dependent manner reduced convulsions or exhibited full protection in MES and PTZ convulsions model, respectively. Interestingly, the protective effects observed for the (R-enantiomer (3 in MES model were significantly greater than those of the standard H3R inverse agonist/antagonist pitolisant, comparable with those observed for PHT, and reversed when rats were pretreated with the selective H3R agonist R-(α-methyl-histamine. Comparisons of the observed antagonistic in vitro affinities among the ligands 1–6 revealed profound stereoselectivity at human H3Rs with varying preferences for this receptor subtype. Moreover, the in vivo anticonvulsant effects observed in this study for ligands 1–6 showed stereoselectivity in different convulsion models in male adult rats. Keywords: histamine, H3 receptor, isomeric antagonists, anticonvulsant activity, stereo­selectivity

  8. Vapor-liquid equilibria for the acetone-ethanol-n-propanol-tert-butanol-water system

    Energy Technology Data Exchange (ETDEWEB)

    Tochigi, K.; Uchida, K.; Kojima, K.

    1981-12-01

    This study deals with the measurement of vapor-liquid equilibria for the five-component system acetone-ethanol-n-propanol-tert-butanol-water at 760 mmHg and prediction of vapor-liquid equilibria by the ASOG group contribution method. The five-component system in this work is composed of a part of the components obtained during ethanol production by vapor-phase hydration of ethylene. 6 refs.

  9. On the application of the NRTL method to ternary (liquid + liquid) equilibria

    International Nuclear Information System (INIS)

    Alvarez Julia, Jorge; Barrero, Carmen R.; Corso, Maria E.; Grande, Maria del Carmen; Marschoff, Carlos M.

    2005-01-01

    The use of the NRTL method for correlating experimental data in ternary (liquid + liquid) equilibria is considered. It is concluded that parameters obtained by direct correlation techniques have not a direct physical meaning. Also, it is shown that the resulting values for these parameters depend on the number of experimental points considered and on the particular calculation method employed. Thus, it is very risky to employ such parameters in predicting equilibria of other ternary mixtures

  10. Calculation of Binary Adsorption Equilibria: Hydrocarbons and Carbon Dioxide on Activated Carbon

    DEFF Research Database (Denmark)

    Marcussen, Lis; Krøll, A.

    1999-01-01

    Binary adsorption equilibria are calculated by means of a mathematical model for multicomponent mixtures combined with the SPD (Spreading Pressure Dependent) model for calculation of activity coefficients in the adsorbed phase. The model has been applied successfully for the adsorption of binary ...... mixtures of hydrocarbons and carbon dioxide on activated carbons. The model parameters have been determined, and the model has proven to be suited for prediction of adsorption equilibria in the investigated systems....

  11. (Vapour + liquid) equilibria for (2,2-dimethoxypropane + methanol) and (2,2-dimethoxypropane + acetone)

    International Nuclear Information System (INIS)

    Jiang Hui; Li Haoran; Wang Congmin; Tan Taijun; Han Shijun

    2003-01-01

    The isothermal and isobaric (vapour + liquid) equilibria for (2,2-dimethoxypropane + methanol) and (2,2-dimethoxypropane + acetone) measured with an inclined ebulliometer are presented. The experimental results are analysed using the UNIQUAC equation with the temperature-dependent binary parameters with satisfactory results. Isobaric (vapour + liquid) equilibria data for these systems at p=99.99 kPa are compared with the literature data. Experimental vapour pressure of 2,2-dimethoxypropane are also included

  12. Elucidation of structural isomers from the homogeneous rhodium-catalyzed isomerization of vegetable oils.

    Science.gov (United States)

    Andjelkovic, Dejan D; Min, Byungrok; Ahn, Dong; Larock, Richard C

    2006-12-13

    The structural isomers formed by the homogeneous rhodium-catalyzed isomerization of several vegetable oils have been elucidated. A detailed study of the isomerization of the model compound methyl linoleate has been performed to correlate the distribution of conjugated isomers, the reaction kinetics, and the mechanism of the reaction. It has been shown that [RhCl(C8H8)2]2 is a highly efficient and selective isomerization catalyst for the production of highly conjugated vegetable oils with a high conjugated linoleic acid (CLA) content, which is highly desirable in the food industry. The combined fraction of the two major CLA isomers [(9Z,11E)-CLA and (10E,12Z)-CLA] in the overall CLA mixture is in the range from 76.2% to 93.4%. The high efficiency and selectivity of this isomerization method along with the straightforward purification process render this approach highly promising for the preparation of conjugated oils and CLA. Proposed improvements in catalyst recovery and reusability will only make this method more appealing to the food, paint, coating, and polymer industries in the future.

  13. Changes in Atmospheric Butanes and Pentanes and Their Isomeric Ratios in the Continental United States

    Science.gov (United States)

    Rossabi, Sam; Helmig, Detlev

    2018-04-01

    Nonmethane hydrocarbons have been used as tracers in research on emissions and atmospheric oxidation chemistry. This research investigates source region mixing ratio trends of the nonmethane hydrocarbons i-butane, n-butane, i-pentane, and n-pentane, and the (i/n) isomeric ratios of these compounds between 2001 and 2015. Data collected at Photochemical Assessment Monitoring Stations, mandated by the U.S. Environmental Protection Agency in ozone nonattainment areas, and data collected at Global Greenhouse Gas Reference Network sites within the National Oceanic and Atmospheric Administration network, and analyzed at the Institute of Arctic and Alpine Research at the University of Colorado-Boulder, were examined. Among all considered species, linear regression analyses on concentration time series had negative slopes at 81% of sites, indicating predominantly declining butane and pentane atmospheric concentrations. Mostly negative slopes (78% of sites) were found for the (i/n) butane and pentane isomeric ratios, including all six and seven statistically significant (i/n) butane and pentane trends, respectively. Over the 15 year investigation period and averaged over all sites, total relative changes were 30 and 45% for the (i/n) ratios of butanes and pentanes, respectively, with a relative increase in the prominence of the n-isomers. Most likely causes include changing isomeric ratios in gasoline sector emissions, and increasing influence of oil and natural gas industry emissions. Changes in concentrations and isomeric ratios depend on proximity of contributing emission sources to measurement sites.

  14. Left atrial isomerism associated with asplenia: prenatal echocardiographic detection of complex congenital cardiac malformations

    NARCIS (Netherlands)

    Stewart, P. A.; Becker, A. E.; Wladimiroff, J. W.; Essed, C. E.

    1984-01-01

    Complex congenital heart disease with suspected isomerism of the atria was diagnosed in two fetuses of 20 and 29 weeks' gestation using two-dimensional and M-mode scanning techniques. The first pregnancy was terminated at 21 weeks' gestation and stillbirth occurred at 31 weeks' gestation in the

  15. Resolution of isomeric new designer stimulants using gas chromatography - Vacuum ultraviolet spectroscopy and theoretical computations

    Czech Academy of Sciences Publication Activity Database

    Škultéty, L'udovít; Fryčák, P.; Qiu, CL.; Smuts, J.; Shear-Laude, L.; Lemr, Karel; Mao, J.X.; Kroll, P.; Schug, K. A.; Szewczak, A.; Vaught, C.; Lurie, I.; Havlíček, Vladimír

    2017-01-01

    Roč. 971, JUNE 8 (2017), s. 55-67 ISSN 0003-2670 R&D Projects: GA MŠk(CZ) LO1509 Institutional support: RVO:61388971 Keywords : Gas phase absorption * Time-dependent density functional theory * Isomeric drugs Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 4.950, year: 2016

  16. Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ligare, Marshall R.; Baker, Erin M.; Laskin, Julia; Johnson, Grant E.

    2017-01-01

    Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

  17. Phase space conduits for reaction in multidimensional systems : HCN isomerization in three dimensions

    NARCIS (Netherlands)

    Waalkens, Holger; Burbanks, Andrew; Wiggins, Stephen

    2004-01-01

    The three-dimensional hydrogen cyanide/isocyanide isomerization problem is taken as an example to present a general theory for computing the phase space structures which govern classical reaction dynamics in systems with an arbitrary (finite) number of degrees of freedom. The theory, which is

  18. The Isomerization of (-)-Menthone to (+)-Isomenthone Catalyzed by an Ion-Exchange Resin

    Science.gov (United States)

    Ginzburg, Aurora L.; Baca, Nicholas A.; Hampton, Philip D.

    2014-01-01

    A traditional organic chemistry laboratory experiment involves the acid-catalyzed isomerization of (-)-menthone to (+)-isomenthone. This experiment generates large quantities of organic and aqueous waste, and only allows the final ratio of isomers to be determined. A "green" modification has been developed that replaces the mineral acid…

  19. The isomerization of allylrhodium intermediates in the rhodium-catalyzed nucleophilic allylation of cyclic imines.

    Science.gov (United States)

    Hepburn, Hamish B; Lam, Hon Wai

    2014-10-20

    Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4-rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene-rhodium complexes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Promotion or suppression of glucose isomerization in subcritical aqueous straight- and branched-chain alcohols.

    Science.gov (United States)

    Gao, Da-Ming; Kobayashi, Takashi; Adachi, Shuji

    2015-01-01

    The influence of water-miscible alcohols (methanol, 1-propanol, 2-propanol, and t-butyl alcohol) on the isomerization of glucose to fructose and mannose was investigated under subcritical aqueous conditions (180-200 °C). Primary and secondary alcohols promoted the conversion and isomerization of glucose to afford fructose and mannose with high and low selectivity, respectively. On the other hand, the decomposition (side-reaction) of glucose was suppressed in the presence of the primary and secondary alcohols compared with that in subcritical water. The yield of fructose increased with increasing concentration of the primary and secondary alcohols, and the species of the primary and secondary alcohols tested had little effect on the isomerization behavior of glucose. In contrast, the isomerization of glucose was suppressed in subcritical aqueous t-butyl alcohol. Both the conversion of glucose and the yield of fructose decreased with increasing concentration of t-butyl alcohol. In addition, mannose was not detected in reactions using subcritical aqueous t-butyl alcohol.

  1. Linkage isomerism in trimeric and polymeric 2,3-cis-procyanindins

    Science.gov (United States)

    Richard W. Hemingway; Lai Yeap Foo; Lawrence J. Porter

    1982-01-01

    Procyanindins polymers consist of chains of 5,7,3',4'-tetrahydroxyflavan-3-ol units linked by C(4)-C(6) or C(4)-C(8) bonds.1 Whereas the procyanidin-B group of dimers are known to exist as pairs of isomers with common flavan-3-ol units, but different interflavanoid linkages,2,3 the extent of such isomerism in...

  2. Polymeric proanthocyanidins: Interflavanoid linkage isomerism in (epicatechin-4)-(epicatechin-4)-catechin procyanidins

    Science.gov (United States)

    Richard W. Hemingway; L. Yeap Foo; L. J. Porter

    1981-01-01

    Procyanidin trimers have been isolated from a variety of plants,1-3 but their structures remain unresolved. We have now isolated three configurational isomers of (epicatechin-4)-(epicatechin-4)-catechin from Pinus taeda L. (loblolly pine) phloem which exhibit isomerism of the interflavanoid linkages.

  3. Palladium Hydride Promoted Stereoselective Isomerization of Unactivated Di(exo)methylenes to Endocyclic Dienes

    OpenAIRE

    Jung, Michael E.; Lee, Gloria S.; Pham, Hung V.; Houk, K. N.

    2014-01-01

    The exomethylenes of 2,6-disubstituted bicyclo[3.3.1]nonan-9-ones 2 are readily isomerized over a palladium catalyst under an atmosphere of hydrogen to predominantly form the isomer 3 with C 2 symmetry with very little formation of the analogous product with C s symmetry. A hydrogen source is essential to effect the rearrangement.

  4. Isomeric Diruthenium Complexes Bridged by Deprotonated Indigo in cis and trans Configuration

    Czech Academy of Sciences Publication Activity Database

    Chatterjee, M.; Ghosh, P.; Beyer, K.; Paretzki, A.; Fiedler, Jan; Kaim, W.; Lahiri, G. K.

    2018-01-01

    Roč. 13, č. 1 (2018), s. 118-125 ISSN 1861-4728 Institutional support: RVO:61388955 Keywords : isomerism * ruthenium * spectroelectrochemistry * structure Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.083, year: 2016

  5. On tokamak equilibria with a zero current or negative current central region

    International Nuclear Information System (INIS)

    Chu, M.S.; Parks, P.B.

    2002-01-01

    Several tokamak experiments have reported the development of a central region with vanishing currents (the current hole). The straightforward application of results from the work of Greene, Johnson and Weimer [Phys. Fluids 14, 671 (1971)] on a tokamak equilibrium to these plasmas leads to the apparent singularities in several physical quantities including the Shafranov shift and casts doubts on the existence of this type of equilibria. In this paper, the above quoted equilibrium theory is re-examined and extended to include equilibria with a current hole. It is shown that singularities can be circumvented and that equilibria with a central current hole do satisfy the magnetohydrodynamic equilibrium condition with regular behavior for all the physical quantities and do not lead to infinitely large Shafranov shifts. Isolated equilibria with negative current in the central region could exist. But equilibria with negative currents in general do not have neighboring equilibria and thus cannot have experimental realization, i.e., no negative currents can be driven in the central region

  6. Photochromic ruthenium sulfoxide complexes: evidence for isomerization through a conical intersection.

    Science.gov (United States)

    McClure, Beth Anne; Mockus, Nicholas V; Butcher, Dennis P; Lutterman, Daniel A; Turro, Claudia; Petersen, Jeffrey L; Rack, Jeffrey J

    2009-09-07

    The complexes [Ru(bpy)(2)(OS)](PF(6)) and [Ru(bpy)(2)(OSO)](PF(6)), where bpy is 2,2'-bipyridine, OS is 2-methylthiobenzoate, and OSO is 2-methylsulfinylbenzoate, have been studied. The electrochemical and photochemical reactivity of [Ru(bpy)(2)(OSO)](+) is consistent with an isomerization of the bound sulfoxide from S-bonded (S-) to O-bonded (O-) following irradiation or electrochemical oxidation. Charge transfer excitation of [Ru(bpy)(2)(OSO)](+) in MeOH results in the appearance of two new metal-to-ligand charge transfer (MLCT) maxima at 355 and 496 nm, while the peak at 396 nm diminishes in intensity. The isomerization is reversible at room temperature in alcohol or propylene carbonate solution. In the absence of light, solutions of O-[Ru(bpy)(2)(OSO)](+) revert to S-[Ru(bpy)(2)(OSO)](+). Kinetic analysis reveals a biexponential decay with rate constants of 5.66(3) x 10(-4) s(-1) and 3.1(1) x 10(-5) s(-1). Cyclic voltammograms of S-[Ru(bpy)(2)(OSO)](+) are consistent with electron-transfer-triggered isomerization of the sulfoxide. Analysis of these voltammograms reveal E(S)(o)' = 0.86 V and E(O)(o)' = 0.49 V versus Ag/Ag(+) for the S- and O-bonded Ru(3+/2+) couples, respectively, in propylene carbonate. We found k(S-->O) = 0.090(15) s(-1) in propylene carbonate and k(S-->O) = 0.11(3) s(-1) in acetonitrile on Ru(III), which is considerably slower than has been reported for other sulfoxide isomerizations on ruthenium polypyridyl complexes following oxidation. The photoisomerization quantum yield (Phi(S-->O) = 0.45, methanol) is quite large, indicating a rapid excited state isomerization rate constant. The kinetic trace at 500 nm is monoexponential with tau = 150 ps, which is assigned to the excited S-->O isomerization rate. There is no spectroscopic or kinetic evidence for an O-bonded (3)MLCT excited state in the spectral evolution of S-[Ru(bpy)(2)(OSO)](+) to O-[Ru(bpy)(2)(OSO)](+). Thus, isomerization occurs nonadiabatically from an S-bonded (or eta(2

  7. Acid-base equilibria inside amine-functionalized mesoporous silica.

    Science.gov (United States)

    Yamaguchi, Akira; Namekawa, Manato; Kamijo, Toshio; Itoh, Tetsuji; Teramae, Norio

    2011-04-15

    Acid-base equilibria and effective proton concentration inside a silica mesopore modified with a trimethyl ammonium (TMAP) layer were studied by steady-state fluorescence experiments. The mesoporous silica with a dense TMAP layer (1.4 molecules/nm(2)) was prepared by a post grafting of N-trimethoxysilylpropyl-N,N,N-trimethylammonium at surfactant-templated mesoporous silica (diameter of silica framework =3.1 nm). The resulting TMAP-modified mesoporous silica strongly adsorbed of anionic fluorescence indicator dyes (8-hydroxypyrene-1,3,6-trisulfonate (pyranine), 8-aminopyrene-1,3,6-trisulfonate (APTS), 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid disulfuric acid (TPPS), 2-naphthol-3,6-disulfonate (2NT)) and fluorescence excitation spectra of these dyes within TMAP-modified mesoporous silica were measured by varying the solution pH. The fluorescence experiments revealed that the acid-base equilibrium reactions of all pH indicator dyes within the TMAP-modified silica mesopore were quite different from those in bulk water. From the analysis of the acid-base equilibrium of pyranine, the following relationships between solution pH (pH(bulk)) and the effective proton concentration inside the pore (pH(pore)) were obtained: (1) shift of pH(pore) was 1.8 (ΔpH(pore)=1.8) for the pH(bulk) change from 2.1 to 9.1 (ΔpH(bulk)=7.0); (2) pH(pore) was not simply proportional to pH(bulk); (3) the inside of the TMAP-modified silica mesopore was suggested to be in a weak acidic or neutral condition when pH(bulk) was changed from 2.0 to 9.1. Since these relationships between pH(bulk) and pH(pore) could explain the acid-base equilibria of other pH indicator dyes (APTS, TPPS, 2NT), these relationships were inferred to describe the effective proton concentration inside the TMAP-modified silica mesopore. © 2011 American Chemical Society

  8. New isomeric states in {sup 152,154,156}Nd produced by spontaneous fission of {sup 252}Cf

    Energy Technology Data Exchange (ETDEWEB)

    Gautherin, C.; Houry, M.; Korten, W.; Le Coz, Y.; Lucas, R.; Phan, X.H.; Theisen, C. [Commissariat l`Energie Atomique de Saclay, Gif sur Yvette (France). DSM/DAPINA/SPhN; Badimon, C.; Barreau, G.; Doan, T.P.; Pedemay, G. [Centre d`Etudes Nucleaires de Bordeaux-Gradignan, Domaine du Haut Vigneau, F-33175 Gradignan (France); Belier, G.; Girod, M.; Meot, V.; Peru, S. [Commissariat a l`Energie Atomique de Bruyeres-le-Chatel, DAM/SPN, BP12, F-91680 Bruyeres-le-Chatel (France); Astier, A.; Ducroux, L.; Meyer, M.; Redon, N. [Institut de Physique Nucleaire de Lyon, F-69622 Villeurbanne Cedex (France)

    1998-04-01

    Isomeric states have been observed in fission-fragments produced by spontaneous fission of {sup 252}Cf. These states are found in neutron rich nuclei of different structure and deformations. About 50 isomeric nuclei have been observed using coincidences between {gamma}-rays identified in EUROGAM II and fission fragments detected in photovoltaic cells (SAPhIR). Lifetimes in the range from 20 ns to 2{mu}s have been measured. Presented calculations based on HFB+D1S force on new measured isomeric states in the {sup 152,154,156}Nd show evidence for K-isomers. (orig.) With 8 figs., 27 refs.

  9. Ion-exchange equilibria and diffusion in engineered backfill

    International Nuclear Information System (INIS)

    Soudek, A.; Jahnke, F.M.; Radke, C.J.

    1984-01-01

    Engineered backfill can add confidence to confinement times of high-level nuclear waste stored in geologic media. This paper discusses the design and operation of a unique radial-flow diffusion cell to determine ion migration rates in backfill material under realistic repository conditions. New experimental results were reported for diffusion of CsCl in a background of NaCl into compacted bentonite and bentonite/quartz mixtures. Representation of the measured diffusion rates by the traditional, homogeneous porous-medium model significantly underestimates cesium penetration distances into the backfill. Surface diffusion is suggested as an additional mechanism by which cations transport in swollen montmorillonite; the surface diffusion coefficients for cesium is determined to be approximately 10 -7 cm 2 /s. An electrostatic site-binding model is developed for ion-exchange equilibria on montmorillonite clay. The effect of pH, ionic strength, and specific adsorption are evaluated and compared favorably to new, experimental exchange isotherms measured on disaggregated clay. The electrostatic site-binding model permits a prediction of the influence of backfill compaction on K/sub d/ values. We find that for strongly adsorbing cations, compactions has little effect. However, anions exhibit significant Donnan exclusion with clay compaction. 40 references, 12 figures

  10. Reduction of Islands in Full-pressure Stellarator Equilibria

    International Nuclear Information System (INIS)

    Hudson, S.R.; Monticello, D.A.; Reiman, A.H.

    2001-01-01

    The control of magnetic islands is a crucial issue in designing Stellarators. Islands are associated with resonant radial magnetic fields at rational rotational-transform surfaces and can lead to chaos and poor plasma confinement. In this article, we show that variations in the resonant fields of a full-pressure stellarator equilibrium can be related to variations in the boundary via a coupling matrix, and inversion of this matrix determines a boundary modification for which the island content is significantly reduced. The numerical procedure is described and the results of island optimization are presented. Equilibria with islands are computed using the Princeton Iterative Equilibrium Solver, and resonant radial fields are calculated via construction of quadratic-flux-minimizing surfaces. A design candidate for the National Compact Stellarator Experiment [Phys. Plasmas 8, 2001], which has a large island, is used to illustrate the technique. Small variations in the boundary shape are used to reduce island size and to reverse the phase of a major island chain

  11. Phase Equilibria of Sn-Co-Cu Ternary System

    Science.gov (United States)

    Chen, Yu-Kai; Hsu, Chia-Ming; Chen, Sinn-Wen; Chen, Chih-Ming; Huang, Yu-Chih

    2012-10-01

    Sn-Co-Cu ternary alloys are promising lead-free solders, and isothermal sections of Sn-Co-Cu phase equilibria are fundamentally important for the alloys' development and applications. Sn-Co-Cu ternary alloys were prepared and equilibrated at 523 K, 1073 K, and 1273 K (250 °C, 800 °C, and 1000 °C), and the equilibrium phases were experimentally determined. In addition to the terminal solid solutions and binary intermetallic compounds, a new ternary compound, Sn3Co2Cu8, was found. The solubilities of Cu in the α-CoSn3 and CoSn2 phases at 523 K (250 °C) are 4.2 and 1.6 at. pct, respectively, while the Cu solubility in the α-Co3Sn2 phase is as high as 20.0 at. pct. The Cu solubility increases with temperature and is around 30.0 at. pct in the β-Co3Sn2 at 1073 K (800 °C). The Co solubility in the η-Cu6Sn5 phase is also significant and is 15.5 at. pct at 523 K (250 °C).

  12. Convergence in gradient systems with branching of equilibria

    International Nuclear Information System (INIS)

    Galaktionov, V A; Pohozaev, Stanislav I; Shishkov, A E

    2007-01-01

    The basic model is a semilinear elliptic equation with coercive C 1 non-linearity: Δψ+f(ψ)=0 in Ω, ψ=0 on ∂Ω, where Ω subset of R N is a bounded smooth domain. The main hypothesis (H R ) about resonance branching is as follows: if a branching of equilibria occurs at a point ψ with k-dimensional kernel of the linearized operator Δ+f'(ψ)I, then the branching subset S k at ψ is a locally smooth k-dimensional manifold. For N=1 the first result on the stabilization to a single equilibrium is due to Zelenyak (1968). It is shown that Zelenyak's approach, which is based on the analysis of Lyapunov functions, can be extended to general gradient systems in Hilbert spaces with smooth resonance branching. The case of asymptotically small non-autonomous perturbations of such systems is also considered. The approach developed here represents an alternative to Hale's stabilization method (1992) and other similar techniques in the theory of gradient systems. Bibliography: 32 titles.

  13. Magnetohydrodynamic equilibria and local stability of axisymmetric tokamak plasmas

    International Nuclear Information System (INIS)

    Peng, Y.K.M.; Dory, R.A.; Nelson, D.B.; Sayer, R.O.

    1976-07-01

    Axisymmetric magnetohydrodynamic equilibria are evaluated in terms of the Mercier Stability Criterion. The parameters of interest include poloidal beta (β/sub p/), current and pressure profile widths, D-shaped and doublet plasmas with elongation (sigma) and triangularity (delta), and the aspect ratio (A). For marginal local stability, the critical values of β, plasma current, and the safety factor q with fixed toroidal field at the geometric center of the plasma are obtained. It is shown that for a wide range of profiles in a D-shaped plasma with A = 3, the highest critical β occurs at β/sub p/ = 2.4, sigma = 1.65, and delta = 0.5. If the toroidal field at the coil surface is fixed, the highest critical pressure occurs near A approximately 3 to 4, given reasonable distance between the coils and the plasma edge. Calculations for a Doublet II-A plasma with sigma = 3 show that with similar pressure profile the highest critical β occurs at β/sub p/ = 1 and is 84 percent of the highest critical β for the D-shaped plasmas. Critical values of ohmic heating power density are also found to be comparable for the two plasma shapes. A D-shaped plasma with the above parameters is suggested for use in future high-β tokamak devices

  14. Spectrum Allocation for Decentralized Transmission Strategies: Properties of Nash Equilibria

    Directory of Open Access Journals (Sweden)

    Peter von Wrycza

    2009-01-01

    Full Text Available The interaction of two transmit-receive pairs coexisting in the same area and communicating using the same portion of the spectrum is analyzed from a game theoretic perspective. Each pair utilizes a decentralized iterative water-filling scheme to greedily maximize the individual rate. We study the dynamics of such a game and find properties of the resulting Nash equilibria. The region of achievable operating points is characterized for both low- and high-interference systems, and the dependence on the various system parameters is explicitly shown. We derive the region of possible signal space partitioning for the iterative water-filling scheme and show how the individual utility functions can be modified to alter its range. Utilizing global system knowledge, we design a modified game encouraging better operating points in terms of sum rate compared to those obtained using the iterative water-filling algorithm and show how such a game can be imitated in a decentralized noncooperative setting. Although we restrict the analysis to a two player game, analogous concepts can be used to design decentralized algorithms for scenarios with more players. The performance of the modified decentralized game is evaluated and compared to the iterative water-filling algorithm by numerical simulations.

  15. Molecular isomerization induced by ultrashort infrared pulses. II. Pump-dump isomerization using pairs of time-delayed half-cycle pulses.

    Science.gov (United States)

    Uiberacker, Christoph; Jakubetz, Werner

    2004-06-22

    We investigate population transfer across the barrier in a double-well potential, induced by a pair of time-delayed single-lobe half-cycle pulses. We apply this setup both to a one-dimensional (1D) quartic model potential and to a three-dimensional potential representing HCN-->HNC isomerization. Overall the results for the two systems are similar, although in the 3D system some additional features appear not seen in the 1D case. The generic mechanism of population transfer is the preparation by the pump pulse of a wave packet involving delocalized states above the barrier, followed by the essentially 1D motion of the delocalized part of wave packet across the barrier, and the eventual de-excitation by the dump pulse to localized states in the other well. The correct timing is given by the well-to-well passage time of the wave packet and its recurrence properties, and by the signs of the field lobes which determine the direction and acceleration or deceleration of the wave packet motion. In the 3D system an additional pump-pump-dump mechanism linked to wave packet motion in the reagent well can mediate isomerization. Since the transfer time and the pulse durations are of the same order of magnitude, there is also a marked dependence of the dynamics and the transfer yield on the pulse duration. Our analysis also sheds light on the pronounced carrier envelope phase dependence previously observed for isomerization and molecular dissociation with one-cycle and sub-one-cycle pulses. (c) 2004 American Institute of Physics.

  16. Distinguishing PCB Isomeric Congeners with their Gas Chromatographic and Mass Spectrometric Ortho Effect using Comprehensive Gas Chromatography

    Science.gov (United States)

    The 209 polychlorinated biphenyl (PCB) congeners and associated nine isomeric groups (nine groups of PCBs with the same degree of chlorination) have been long recorded as high endocrine disrupting chemicals in the environment. Difficult analytical problems exist, in those frequen...

  17. Communication: An accurate calculation of the S1 C2H2 cis-trans isomerization barrier height

    International Nuclear Information System (INIS)

    Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.

    2016-01-01

    A high level ab initio calculation of the cis-trans isomerization barrier height in the first excited singlet electronic state of acetylene is found to agree very well with a recent experimental determination.

  18. The feasibility of parameterizing four-state equilibria using relaxation dispersion measurements

    International Nuclear Information System (INIS)

    Li Pilong; Martins, Ilídio R. S.; Rosen, Michael K.

    2011-01-01

    Coupled equilibria play important roles in controlling information flow in biochemical systems, including allosteric molecules and multidomain proteins. In the simplest case, two equilibria are coupled to produce four interconverting states. In this study, we assessed the feasibility of determining the degree of coupling between two equilibria in a four-state system via relaxation dispersion measurements. A major bottleneck in this effort is the lack of efficient approaches to data analysis. To this end, we designed a strategy to efficiently evaluate the smoothness of the target function surface (TFS). Using this approach, we found that the TFS is very rough when fitting benchmark CPMG data to all adjustable variables of the four-state equilibria. After constraining a portion of the adjustable variables, which can often be achieved through independent biochemical manipulation of the system, the smoothness of TFS improves dramatically, although it is still insufficient to pinpoint the solution. The four-state equilibria can be finally solved with further incorporation of independent chemical shift information that is readily available. We also used Monte Carlo simulations to evaluate how well each adjustable parameter can be determined in a large kinetic and thermodynamic parameter space and how much improvement can be achieved in defining the parameters through additional measurements. The results show that in favorable conditions the combination of relaxation dispersion and biochemical manipulation allow the four-state equilibrium to be parameterized, and thus coupling strength between two processes to be determined.

  19. Efficient assembly of polysubstituted pyrroles via a (3 + 2) cycloaddition/skeletal rearrangement/redox isomerization cascade reaction.

    Science.gov (United States)

    Yu, Yuanyuan; Wang, Chunyu; He, Xinze; Yao, Xiaotong; Zu, Liansuo

    2014-07-03

    An unprecedented cascade strategy, used in conjunction with a redox isomerization, for the synthesis of 3-allyl pyrroles is reported. In a single step, readily accessible simple starting materials are transformed into highly substituted pyrroles with high efficiency. The products obtained contain allyl substituents, which can be readily elaborated to other useful functional groups. The reaction proceeds through an unusual (3 + 2) cycloaddition/skeletal rearrangement/redox isomerization pathway.

  20. Theory of equilibria of elastic 2-braids with interstrand interaction

    Science.gov (United States)

    Starostin, E. L.; van der Heijden, G. H. M.

    2014-03-01

    Motivated by continuum models for DNA supercoiling we formulate a theory for equilibria of 2-braids, i.e., structures formed by two elastic rods winding around each other in continuous contact and subject to a local interstrand interaction. No assumption is made on the shape of the contact curve. The theory is developed in terms of a moving frame of directors attached to one of the strands. The other strand is tracked by including in this frame the normalised closest-approach chord connecting the two strands. The kinematic constant-distance constraint is formulated at strain level through the introduction of what we call braid strains. As a result the total potential energy involves arclength derivatives of these strains, thus giving rise to a second-order variational problem. The Euler-Lagrange equations for this problem give balance equations for the overall braid force and moment referred to the moving frame as well as differential equations that can be interpreted as effective constitutive relations encoding the effect that the second strand has on the first as the braid deforms under the action of end loads. Hard contact models are used to obtain the normal contact pressure between strands that has to be non-negative for a physically realisable solution without the need for external devices such as clamps or glue to keep the strands together. The theory is first illustrated by a number of problems that can be solved analytically and then applied to several new problems that have not hitherto been treated.

  1. Isotopic equilibria between sulphur solute species at high temperature

    International Nuclear Information System (INIS)

    Robinson, B.W.

    1978-01-01

    Sulphur solute species in ore solutions and geothermal discharges include HSO 4 - , SO 4 2- , H 2 S, and HS - , as well as the ion-paired species, NaHS 0 , NaHSO 4 - and Na 2 SO 4 0 . Observed sulphate-sulphide fractionation factors and the rates of attainment of isotopic equilibrium are likely to depend on the nature of the sulphur species actually taking part in these isotopic equilibria. Preliminary experiments in alkaline solution (pH 10.1 at 20 0 C) were carried out in a gold cell. No significant isotope fractionation was observed between the SO 4 2- and HS - in 29 days at 200 0 C, 63days at 300 0 C, or 90 days at 250 0 C. However, similar experiments at 350 0 C in sealed gold capsules at room temperature pH 8.5 showed slow exchange(t( 1 / 2 ) was calculated to be 510 days for the SO 4 2- -HS - exchange reaction using the theoretical fractionation of 20.2 0 / 00 ). The addition of NaCl appeared to have no affect on the exchange. However, pH strongly controls the reaction rate, and exchange probably involves H 2 S and the HSO 4 - ion. Additional preliminary experiments were conducted with a fivefold increase in the sulphur concentration; a decrease in t( 1 / 2 ) to 142 days resulted. Some inter-relationship between sulphur concentration and exchange rate thus exists. The important controlling parameters of isotope exchange (temperature, pH, and ΣS) can be seen to have influenced exchange in natural systems.(auth.)

  2. Longitudinal traveling waves bifurcating from Vlasov plasma equilibria

    International Nuclear Information System (INIS)

    Holloway, J.P.

    1989-01-01

    The kinetic equations governing longitudinal motion along a straight magnetic field in a multi-species collisionless plasma are investigated. A necessary condition for the existence of small amplitude spatially periodic equilibria and traveling waves near a given spatially uniform background equilibrium is derived, and the wavelengths which such solutions must approach as their amplitude decreases to zero are discussed. A sufficient condition for the existence of these small amplitude waves is also established. This is accomplished by studying the nonlinear ODE for the potential which arises when the distribution functions are represented in a BGK form; the arbitrary functions of energy that describe the BGK representation are tested as an infinite dimensional set of parameters in a bifurcation theory for the ODE. The positivity and zero current condition in the wave frame of the BGK distribution functions are maintained. The undamped small amplitude nonlinear waves so constructed can be made to satisfy the Vlasov dispersion relation exactly, but in general they need only satisfy it approximately. Numerical calculations reveal that even a thermal equilibrium electron-proton plasma with equal ion and electron temperatures will support undamped traveling waves with phase speeds greater than 1.3 times the electron velocity; the dispersion relation for this case exhibits both Langmuir and ion-acoustic branches as long wavelength limits, and shows how these branches are in fact connected by short wavelength waves of intermediate frequency. In apparent contradiction to the linear theory of Landau, these exact solutions of the kinetic equations do not damp; this contradiction is explained by observing that the linear theory is, in general, fundamentally incapable of describing undamped traveling waves

  3. Observation of excited states and isomeric decays in doubly-odd 208Fr

    International Nuclear Information System (INIS)

    Kanjilal, D.; Bhattacharya, S.; Goswami, A.; Kshetri, R.; Raut, R.; Saha, S.; Bhowmik, R.K.; Gehlot, J.; Jnaneswari, G.; Muralithar, S.; Singh, R.P.; Mukherjee, B.; Mukherjee, G.

    2009-01-01

    The nuclei near the doubly magic 208 Pb are predicted to exhibit various interesting structural phenomena, one of which is a wealth of isomerism. However, a detailed study of high spin states of 211, 212, 213 Fr has already been done. Structure of such trans-Lead nuclei can be interpreted in terms of the shell model states, and the high spin states of these nuclei are interpreted. One of the major interests in the spectroscopic investigation of these nuclei is the role played by the i 13/2 state in creating isomeric levels which decay through transitions of higher muiltipolarity, or are hindered by the close proximity of the levels below. A systematic study of these nuclei will possibly reveal many other interesting structural features

  4. Synthesis of Isomeric Phosphoubiquitin Chains Reveals that Phosphorylation Controls Deubiquitinase Activity and Specificity

    Directory of Open Access Journals (Sweden)

    Nicolas Huguenin-Dezot

    2016-07-01

    Full Text Available Ubiquitin is post-translationally modified by phosphorylation at several sites, but the consequences of these modifications are largely unknown. Here, we synthesize multi-milligram quantities of ubiquitin phosphorylated at serine 20, serine 57, and serine 65 via genetic code expansion. We use these phosphoubiquitins for the enzymatic assembly of 20 isomeric phosphoubiquitin dimers, with different sites of isopeptide linkage and/or phosphorylation. We discover that phosphorylation of serine 20 on ubiquitin converts UBE3C from a dual-specificity E3 ligase into a ligase that primarily synthesizes K48 chains. We profile the activity of 31 deubiquitinases on the isomeric phosphoubiquitin dimers in 837 reactions, and we discover that phosphorylation at distinct sites in ubiquitin can activate or repress cleavage of a particular linkage by deubiquitinases and that phosphorylation at a single site in ubiquitin can control the specificity of deubiquitinases for distinct ubiquitin linkages.

  5. Multi-quasiparticle high-K isomeric states in deformed nuclei

    Directory of Open Access Journals (Sweden)

    Xu F. R.

    2016-01-01

    Full Text Available In the past years, we have made many theoretical investigations on multi-quasiparticle high-K isomeric states. A deformation-pairing-configuration self-consistent calculation has been developed by calculating a configuration-constrained multi-quasiparticle potential energy surface (PES. The specific single-particle orbits that define the high-K configuration are identified and tracked (adiabatically blocked by calculating the average Nilsson numbers. The deformed Woods-Saxon potential was taken to give single-particle orbits. The configuration-constrained PES takes into account the shape polarization effect. Such calculations give good results on excitation energies, deformations and other structure information about multi-quasiparticle high-K isomeric states. Many different mass regions have been investigated.

  6. [Isomeric derivatives of lupinine and epilupinine--organophosphorus inhibitors of cholinesterases].

    Science.gov (United States)

    Basova, N E; Kormilitsyn, B N; Perchenok, A Iu; Rosengart, E V; Saakov, V S; Suvorov, A A

    2012-01-01

    The isomeric-structure analysis data of anticholinesterase action of organophosphorous inhibitors with similar structure help in the search of specific effectors and detection of differences in reactivity of various animals' enzymes. This study compared the data of efficacy in respect of 4 mammal and 5 arthropoda cholinesterase preparations for 26 quinolizidine inhibitors, which molecules contain both the isomeric unbranched and branched alkoxyl radicals in the phosphoryl group, and the epimeric lupinine and epilupinine derivatives in the leaving group. The changes in the alkoxyl radical structure of inhibitor molecules act on their efficacy only with respect to the mammal enzymes ("group" inhibitor specificity). The differences between lupinine and epilupinine derivatives were revealed. Highly specific inhibitors of different enzymes were detected among the tested compounds.

  7. An isomerization-induced cage-breaking process in a molecular glass former below Tg

    International Nuclear Information System (INIS)

    Teboul, V.; Saiddine, M.; Accary, J.-B.; Nunzi, J.-M.

    2011-01-01

    A recent experimental [P. Karageorgiev, D. Neher, B. Schulz, B. Stiller, U. Pietsch, M. Giersig, L. Brehmer, Nature Mater. 4, 699 (2005)] study has found liquidlike diffusion below the glass-transition temperature in azobenzene-containing materials under irradiation. This result suggests that the isomerization-induced massive mass transport that leads to surface relief gratings formation in these materials, is induced by this huge increase of the matrix diffusion coefficient around the probe. In order to investigate the microscopic origin of the increase of the diffusion, we use molecular dynamics simulations of the photoisomerization of probe dispersed red 1 molecules dispersed inside a glassy molecular matrix. Results show that the increased diffusion is due to an isomerization-induced cage-breaking process. A process that explains the induced cooperative motions recently observed in these photoactive materials.

  8. Catalytic Isomerization of Dihydroxyacetone to Lactic Acid and Alkyl Lactates over Hierarchical Zeolites Containing Tin

    Directory of Open Access Journals (Sweden)

    Agnieszka Feliczak-Guzik

    2018-01-01

    Full Text Available Hierarchical zeolites containing tin were obtained, characterized and used in a reaction of catalytic isomerization of dihydroxyacetone (DHA to lactic acid and alkyl lactates. These catalysts are characterized by preserved crystallinity and primary microporosity with the simultaneous existence of secondary porosity regarding mesopores, which facilitates access of large molecules of reagents to active centers. Creation of additional porosity was confirmed by X-ray diffraction and low-temperature nitrogen adsorption/desorption studies. The reaction of dihydroxyacetone isomerization was conducted in different reaction media such as methanol, ethanol or water with the use of two heating methods: microwave radiation and conventional heating. The application of microwave radiation enabled to reduce the reaction time to 1 h and achieve dihydroxyacetone conversion of >90% and high yields of the desired reaction products.

  9. Measurement of millisecond half-lives of isomeric levels in some nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Garg, K C; Khurana, C S [Punjabi Univ., Patiala (India). Nuclear Science Labs.

    1976-09-01

    Half-lives of 2.7, 14.5, 17, 20, 20.4, 44 and 2230 msec, of isomeric levels in /sup 208/Bi, /sup 88/Y, /sup 75/As, /sup 24/Na, /sup 71/Ge, /sup 114/In and /sup 167/Er respectively have been measured, employing on-line irradiation system. These millisecond isomeric levels are produced by 14.7 MeV neutrons through (n,p), (n,..cap alpha..), (n,n') and (n,2n) reactions on natural target samples. A ..gamma..-ray scintillation detector coupled with NTA-512B, 1024 channel analyzer has been used to follow the decay of the millisecond activities. Deflected deuteron beam bursts have been used to reduce the long-time background to initial count ratios in the decay curves to achieve a better accuracy of measurements.

  10. Collective coordinates and an accompanying metric force in structural isomerization dynamics of molecules

    International Nuclear Information System (INIS)

    Yanao, Tomohiro; Takatsuka, Kazuo

    2003-01-01

    Structural isomerization dynamics of three- and four-atom clusters of vanishing total angular momentum is studied in terms of internal coordinates of n-body systems on the basis of a gauge theory. The so-called principal-axis hyperspherical coordinates are employed effectively as collective variables for the study of isomerization reactions. It turns out that the non-Euclidean metric on the internal space gives rise to a force, which works in response to internal motions called the democratic (kinematic) rotations in the internal space. This metric force generally tends to induce an asymmetry in mass balance of a system, and is coupled with the usual potential force to give rise to trapped motions in the vicinity of the transition states of the cluster. This observation provides a different perspective for the so-called recrossing problem in chemical reaction dynamics

  11. A novel base-induced isomerization gives access to unprecedented (E)-exo-glycals.

    Science.gov (United States)

    Eppe, Guillaume; Dumitrescu, Lidia; Pierrot, Olivier; Li, Tianlei; Pan, Weidong; Vincent, Stéphane P

    2013-08-26

    Bump the base: This study reports the discovery of the base-induced Z-to-E isomerization of exo-glycals bearing an electron-withdrawing group (EWG). The scope of this novel transformation regarding the carbohydrate unit is also discussed. After elucidating the mechanism, preparation of novel (E)-exo- glycals was performed (TBS = tert-butyldimethylsilyl). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Internal conversion of the (13/2+→5/2-) isomeric transition in 199Hg

    International Nuclear Information System (INIS)

    Radha Krishna, K.; Chandrasekhar Rao, M.V.S.; Sree Krishna Murty, G.; Venkateswara Rao, N.; Bhuloka Reddy, S.; Satyanarayana, G.; Sastry, D.L.; Iyer, M.R.; Sahasrabhude, S.G.

    1990-01-01

    The total conversion coefficient of the M4 transition (374 KeV) in the decay of the 13/2 + isomeric state to 5/2 - state in 199 Hg measured using the relative gamma intensity method α T is determined to be 6.34 ± 0.29 in agreement with the theory due to Rosel et al. (author). 1 tab., 3 figs., 11 refs

  13. Sugar Profile, Mineral Content, and Rheological and Thermal Properties of an Isomerized Sweet Potato Starch Syrup

    OpenAIRE

    Dominque, Brunson; Gichuhi, Peter N.; Rangari, Vijay; Bovell-Benjamin, Adelia C.

    2013-01-01

    Currently, corn is used to produce more than 85% of the world's high fructose syrup (HFS). There is a search for alternative HFS substrates because of increased food demand and shrinking economies, especially in the developing world. The sweet potato is a feasible, alternative raw material. This study isomerized a high glucose sweet potato starch syrup (SPSS) and determined its sugar profile, mineral content, and rheological and thermal properties. Rheological and thermal properties were meas...

  14. {sup 13}C-NMR studies on disulfide bond isomerization in bovine pancreatic trypsin inhibitor (BPTI)

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Mitsuhiro [Kumamoto University, Department of Structural BioImaging, Faculty of Life Sciences (Japan); Miyanoiri, Yohei [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan); Terauchi, Tsutomu [Tokyo Metropolitan University, Graduate School of Science and Engineering (Japan); Kainosho, Masatsune, E-mail: kainosho@tmu.ac.jp [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan)

    2016-09-15

    Conformational isomerization of disulfide bonds is associated with the dynamics and thus the functional aspects of proteins. However, our understanding of the isomerization is limited by experimental difficulties in probing it. We explored the disulfide conformational isomerization of the Cys14–Cys38 disulfide bond in bovine pancreatic trypsin inhibitor (BPTI), by performing an NMR line-shape analysis of its Cys carbon peaks. In this approach, 1D {sup 13}C spectra were recorded at small temperature intervals for BPTI samples selectively labeled with site-specifically {sup 13}C-enriched Cys, and the recorded peaks were displayed in the order of the temperature after the spectral scales were normalized to a carbon peak. Over the profile of the line-shape, exchange broadening that altered with temperature was manifested for the carbon peaks of Cys14 and Cys38. The Cys14–Cys38 disulfide bond reportedly exists in equilibrium between a high-populated (M) and two low-populated states (m{sub c14} and m{sub c38}). Consistent with the three-site exchange model, biphasic exchange broadening arising from the two processes was observed for the peak of the Cys14 α-carbon. As the exchange broadening is maximized when the exchange rate equals the chemical shift difference in Hz between equilibrating sites, semi-quantitative information that was useful for establishing conditions for {sup 13}C relaxation dispersion experiments was obtained through the carbon line-shape profile. With respect to the m{sub c38} isomerization, the {sup 1}H-{sup 13}C signals at the β-position of the minor state were resolved from the major peaks and detected by exchange experiments at a low temperature.

  15. Model-Based Analysis and Efficient Operation of a Glucose Isomerization Reactor Plant

    DEFF Research Database (Denmark)

    Papadakis, Emmanouil; Madsen, Ulrich; Pedersen, Sven

    2015-01-01

    efficiency. The objective of this study is the application of the developed framework on an industrial case study of a glucose isomerization (GI) reactor plant that is part of a corn refinery, with the objective to improve the productivity of the process. Therefore, a multi-scale reactor model...... is developedfor use as a building block for the GI reactor plant simulation. An optimal operation strategy is proposed on the basis of the simulation results...

  16. Isomeric cross section ratios in 55Mn(α, n)58m,gCo reaction

    International Nuclear Information System (INIS)

    Long Xianguan; He Fuqing; Peng Xiufen; Liu Mantian

    1989-01-01

    The isomeric cross section ratios in 55 Mn(α, n) 58m,g Co reaction are measured for incident alpha-particle energies ranging from 10.4 to 26.5 MeV by using activation method and stacked-foil technique. The measured values are compared with theoretical calculations performed by using Huizenga and Vandenbosch method and the values of spin cutoff factor are obtained for product nucleus 58 Co

  17. High spin states in 63Cu. 17/2+ isomeric yrast state

    International Nuclear Information System (INIS)

    Tsan Ung Chan; Bruandet, J.F.; Dauchy, A.; Giorni, A.; Glasser, F.; Morand, C.; Chambon, B.; Drain, D.

    1979-01-01

    The 63 Cu nucleus has been studied via the reaction 61 Ni(α, pnγ), using different in beam γ spectroscopy techniques. An isomeric high-spin Yrast state 17/2 + (tau = 6.1 +- 0.6ns) is located at 4498 keV. The gsub(9/2) shell must be involved to explain positive high-spin states established in this work [fr

  18. [Photoionization ion mobility spectrometry (UV-IMS) for the isomeric volatile organic compounds].

    Science.gov (United States)

    Li, Hu; Niu, Wen-qi; Wang, Hong-mei; Huang, Chao-qun; Jiang, Hai-he; Chu, Yan-nan

    2012-01-01

    The construction and performance study is reported for a newly developed ultraviolet photoionization ion mobility spectrometry (UV-IMS). In the present paper, an UV-IMS technique was firstly developed to detect eleven isomeric volatile organic compounds including the differences in the structure of carbon chain, the style of function group and the position of function group. Their reduced mobility values were determined and increased in this order: linears alcohols homemade UV-IMS was around ppb-ppm.

  19. High spin states and isomeric decays in doubly-odd {sup 208}Fr

    Energy Technology Data Exchange (ETDEWEB)

    Kanjilal, D.; Bhattacharya, S.; Goswami, A.; Kshetri, R.; Raut, R. [Nuclear and Atomic Physics Division, Saha Institute of Nuclear Physics, Kolkata 700064 (India); Saha, S., E-mail: satyajit.saha@saha.ac.i [Nuclear and Atomic Physics Division, Saha Institute of Nuclear Physics, Kolkata 700064 (India); Bhowmik, R.K.; Gehlot, J.; Muralithar, S.; Singh, R.P. [Inter University Accelerator Centre, New Delhi 110067 (India); Jnaneswari, G. [Department of Physics, Andhra University, Vishakhapatnam 530003 (India); Mukherjee, G. [Variable Energy Cyclotron Centre, Kolkata 700064 (India); Mukherjee, B. [Department of Physics, Visva Bharati, Santiniketan 731235 (India)

    2010-10-15

    Neutron deficient isotopes of francium (Z=87, N{approx}121-123) as excited nuclei were produced in the fusion-evaporation reaction: {sup 197}Au({sup 16}O, xn) {sup 213-x}Fr at 100 MeV. The {gamma} rays from the residues were observed through the high sensitivity Germanium Clover detector array INGA. The decay of the high spin states and the isomeric states of the doubly-odd {sup 208}Fr nuclei, identified from the known sequence of ground state transitions, were observed. The half-lives of the E{sub {gamma}=}194(2) keV isomeric transition, known from earlier observations, was measured to be T{sub 1/2}=233(18) ns. A second isomeric transition at E{sub {gamma}=}383(2) keV and T{sub 1/2}=33(7) ns was also found. The measured half-lives were compared with the corresponding single particle estimates, based on the level scheme obtained from the experiment.

  20. The study of a new short-life isomeric state in 38K

    International Nuclear Information System (INIS)

    Iordachescu, A.

    1976-01-01

    The 38 K nucleus having a protone and neutron hole coupled with a 40 Ca inert core has a structure analysed easily by the shell model. A new short life, high spin and highly excited isomeric state of the 38 K nucleus has been studied in detail using this model. Theoretical aspects connected with static and dynamic electromagnetic moments of the nucleus state, with the magnetic moment of the nucleus and the selection rules according to the isotopic spin are presented in the case of gamma transitions. Experimentallz/ presented in the case of gamma transitions. Experimentally, it has been used a combination between a natural pulsation of the cyclotron beam and an external pulsation by electrostatic deflexion, thus obtaining a pulsation beam of 12-26 MeV alpha particles. As targets, a series of chemical chlorine combinations have been utilized, the isomeric state being obtained by the reaction 35 Cl(α,n) 38 K, having the isomeric level (1fsub(7/2))sub(7+)sup(2). (author)

  1. Discussion of isomeric ratios in (p, n) and (d, 2n) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Bakhshiyan, T. M., E-mail: tiruhi44@mail.ru [Yerevan State University (Armenia)

    2016-01-15

    Isomeric ratios (IR) in the (p, n) and (d, 2n) reactions are considered. The dependence of IR values on the projectile type and energy, the target- and product-nucleus spin, the spin difference between the isomeric and ground states of products, and the product mass number is discussed. The isomeric ratios for 46 product nuclei (from {sup 44m,g}Sc to {sup 127m,g}Xe) obtained in reactions where target and product nuclei have identical mass numbers were calculated at energies from the reaction threshold to 50 MeV (with a step of ΔE = 1 MeV). The calculations in question were performed with the aid of the TALYS 1.4 code package. The calculated IR values were compared with their experimental counterparts available from the literature (EXFOR database). In the majority of cases, the calculated IR values agree well with the experimental data in question. It is noteworthy that the IR values obtained in (d, 2n) reactions are substantially greater than those in (p, n) reactions.

  2. Photo-isomerization and oxidation of bilirubin in mammals is dependent on albumin binding.

    Science.gov (United States)

    Goncharova, Iryna; Jašprová, Jana; Vítek, Libor; Urbanová, Marie

    2015-12-01

    The bilirubin (BR) photo-conversion in the human body is a protein-dependent process; an effective photo-isomerization of the potentially neurotoxic Z,Z-BR as well as its oxidation to biliverdin in the antioxidant redox cycle is possible only when BR is bound on serum albumin. We present a novel analytical concept in the study of linear tetrapyrroles metabolic processes based on an in-depth mapping of binding sites in the structure of human serum albumin (HSA). A combination of fluorescence spectroscopy, circular dichroism (CD) spectroscopy, and molecular modeling methods was used for recognition of the binding site for BR, its derivatives (mesobilirubin and bilirubin ditaurate), and the products of the photo-isomerization and oxidation (lumirubin, biliverdin, and xanthobilirubic acid) on HSA. The CD spectra and fluorescent quenching of the Trp-HSA were used to calculate the binding constants. The results of the CD displacement experiments performed with hemin were interpreted together with the findings of molecular docking performed on the pigment-HSA complexes. We estimated that Z,Z-BR and its metabolic products bind on two independent binding sites. Our findings support the existence of a reversible antioxidant redox cycle for BR and explain an additional pathway of the photo-isomerization process (increase of HSA binding capacity; the excess free [unbound] BR can be converted and also bound to HSA). Copyright © 2015 Elsevier Inc. All rights reserved.

  3. Spectroscopic and Theoretical Identification of Two Thermal Isomerization Pathways for Bistable Chiral Overcrowded Alkenes.

    Science.gov (United States)

    Kistemaker, Jos C M; Pizzolato, Stefano F; van Leeuwen, Thomas; Pijper, Thomas C; Feringa, Ben L

    2016-09-12

    Chiroptical molecular switches play an important role in responsive materials and dynamic molecular systems. Here we present the synthesis of four chiral overcrowded alkenes and the experimental and computational study of their photochemical and thermal behavior. By irradiation with UV light, metastable diastereoisomers with opposite helicity were generated through high yielding E-Z isomerizations. Kinetic studies on metastable 1-4 using CD spectroscopy and HPLC analysis revealed two pathways at higher temperatures for the thermal isomerization, namely a thermal E-Z isomerization (TEZI) and a thermal helix inversion (THI). These processes were also studied computationally whereby a new strategy was developed for calculating the TEZI barrier for second-generation overcrowded alkenes. To demonstrate that these overcrowded alkenes can be employed as bistable switches, photochromic cycling was performed, which showed that the alkenes display good selectivity and fatigue resistance over multiple irradiation cycles. In particular, switch 3 displayed the best performance in forward and backward photoswitching, while 1 excelled in thermal stability of the photogenerated metastable form. Overall, the alkenes studied showed a remarkable and unprecedented combination of switching properties including dynamic helicity, reversibility, selectivity, fatigue resistance, and thermal stability. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Preclinical Evaluation of the Synthetic Adjuvant SQS-21 and its Constituent Isomeric Saponins

    Science.gov (United States)

    Ragupathi, Govind; Damani, Payal; Deng, Kai; Adams, Michelle M.; Hang, Jianfeng; George, Constantine; Livingston, Philip O.; Gin, David Y.

    2010-01-01

    The saponin fraction QS-21 from Quillaja saponaria has been demonstrated to be a potent immunological adjuvant when mixed with keyhole limpet hemocyanin conjugate vaccines, as well as with other classes of subunit antigen vaccines. QS-21 adjuvant is composed of two isomers that include the apiose and xylose forms in a ratio of 65:35, respectively. The chemical syntheses of these two isomers in pure form have recently been disclosed. Herein we describe detailed in vivo immunological evaluations of these synthetic QS-21 isomeric constituents, employing the GD3-KLH melanoma antigen. With this vaccine construct, high antibody titers against GD3 ganglioside and KLH were elicited when GD3-KLH was co-administered with adjuvant, either as the individual separate synthetic QS-21 isomers (SQS-21-Api or SQS-21-Xyl), or as its reconstituted 65:35 isomeric mixture (SQS-21). These antibody titer levels were comparable to that elicited by vaccinations employing naturally derived QS-21 (PQS-21). Moreover, toxicities of the synthetic saponin adjuvants were also found to be comparable to that of naturally derived PQS-21. These findings demonstrate unequivocally that the adjuvant activity of QS-21 resides in these two principal isomeric forms, and not in trace contaminants within the natural extracts. This lays the foundation for future exploration of structure-function correlations to enable the discovery of novel saponins with increased potency, enhanced stability, and attenuated toxicity. PMID:20450868

  5. Thermal isomerization of azobenzenes: on the performance of Eyring transition state theory

    Science.gov (United States)

    Rietze, Clemens; Titov, Evgenii; Lindner, Steven; Saalfrank, Peter

    2017-08-01

    The thermal Z\\to E (back-)isomerization of azobenzenes is a prototypical reaction occurring in molecular switches. It has been studied for decades, yet its kinetics is not fully understood. In this paper, quantum chemical calculations are performed to model the kinetics of an experimental benchmark system, where a modified azobenzene (AzoBiPyB) is embedded in a metal-organic framework (MOF). The molecule can be switched thermally from cis to trans, under solvent-free conditions. We critically test the validity of Eyring transition state theory for this reaction. As previously found for other azobenzenes (albeit in solution), good agreement between theory and experiment emerges for activation energies and activation free energies, already at a comparatively simple level of theory, B3LYP/6-31G* including dispersion corrections. However, theoretical Arrhenius prefactors and activation entropies are in qualitiative disagreement with experiment. Several factors are discussed that may have an influence on activation entropies, among them dynamical and geometric constraints (imposed by the MOF). For a simpler model—Z\\to E isomerization in azobenzene—a systematic test of quantum chemical methods from both density functional theory and wavefunction theory is carried out in the context of Eyring theory. Also, the effect of anharmonicities on activation entropies is discussed for this model system. Our work highlights capabilities and shortcomings of Eyring transition state theory and quantum chemical methods, when applied for the Z\\to E (back-)isomerization of azobenzenes under solvent-free conditions.

  6. Concurrent Mass Measurement and Laser Spectroscopy for Unambiguous Isomeric State Assignment

    Science.gov (United States)

    Lascar, Daniel; Babcock, Carla; Henderson, Jack; Pearson, Matt

    2017-09-01

    Recent work by the TITAN group at TRIUMF on isomeric state mass measurements of odd-A, neutron-rich cadmium nuclei has shown a disconnect between experiment and theory in 127 g , mCd. The spin and parity assignments of the ground and isomeric states are assigned as 3/2+ and 11/2-, respectively, primarily via systematic arguments. Conversely, state of the art shell model and ab initio calculations show a reversal of the states, predicting a ground state of 11/2- and a 3/2+ isomer. Penning Trap Mass Spectrometry (PTMS) can measure the energy separation between the ground state and the isomer without ambiguity but cannot, on its own, comment on the spin and parity. Collinear Laser Spectroscopy (CLS) experiments have been performed on 127Cd and have elegantly demonstrated the existence of both 3/2+ and 11/2- states. What CLS cannot do, on its own, is assign an ordering to those states. If, however, a PTMS and CLS experiment could be performed concurrently using identical beams from the same facility then there exists sufficient information shared between both experiments that a definitive assignment can be made. We present a concept for a new slate of measurements using existing experimental facilities simultaneously, with shared resources, to definitively assign spin and parity for ground and isomeric states in short-lived nuclei.

  7. Yields and isomeric ratio of xenon and krypton isotopes from thermal neutron fission of 235U

    International Nuclear Information System (INIS)

    Hsu, S.S.; Lin, J.T.; Yang, C.M.; Yu, Y.W.

    1981-01-01

    The experimental cumulative yields of 85 Kr/sup m/, 87 Kr, 88 Kr, 133 Xe/sup g/, 135 Xe/sup m/, and 135 Xe/sup g/ and the independent isomeric yield of 133 Xe/sup m/ in the thermal neutron fission of 235 U have been measured by the gas chromatographic method. The independent yields of 133 Xe/sup g/, 135 Xe/sup m/, and 135 Xe/sup g/ were deduced with the aid of 133 I and 135 I data. The isomeric yield ratios of 133 Xe and 135 Xe have been computed and compared with theoretical values since they have the same high spin state J = 11/2 - and low spin ground state J = 3/2 + . The influence of the shell effect on the fission isomeric yield ratio is discussed. From the measured independent yield of Xe isotopes plus the reported data, the Xe-isotopic distribution curve has been constructed. The curve is compared with the isotopic distribution curves of Xe isotopes formed in 11.5 GeV proton interactions with 238 U and Cs isotopes formed in 24 GeV proton interactions with 238 U. Upon fitting the yield curves we find that only those products with N/Z> or =1.48 fit a curve typical of a binary fission process

  8. Non-existence of Normal Tokamak Equilibria with Negative Central Current

    International Nuclear Information System (INIS)

    Hammett, G.W.; Jardin, S.C.; Stratton, B.C.

    2003-01-01

    Recent tokamak experiments employing off-axis, non-inductive current drive have found that a large central current hole can be produced. The current density is measured to be approximately zero in this region, though in principle there was sufficient current-drive power for the central current density to have gone significantly negative. Recent papers have used a large aspect-ratio expansion to show that normal MHD equilibria (with axisymmetric nested flux surfaces, non-singular fields, and monotonic peaked pressure profiles) can not exist with negative central current. We extend that proof here to arbitrary aspect ratio, using a variant of the virial theorem to derive a relatively simple integral constraint on the equilibrium. However, this constraint does not, by itself, exclude equilibria with non-nested flux surfaces, or equilibria with singular fields and/or hollow pressure profiles that may be spontaneously generated

  9. A Continuous Family of Equilibria in Ferromagnetic Media are Ground States

    Science.gov (United States)

    Su, Xifeng; de la Llave, Rafael

    2017-09-01

    We show that a foliation of equilibria (a continuous family of equilibria whose graph covers all the configuration space) in ferromagnetic transitive models are ground states. The result we prove is very general, and it applies to models with long range and many-body interactions. As an application, we consider several models of networks of interacting particles including models of Frenkel-Kontorova type on Z^d and one-dimensional quasi-periodic media. The result above is an analogue of several results in the calculus of variations (fields of extremals) and in PDE's. Since the models we consider are discrete and long range, new proofs need to be given. We also note that the main hypothesis of our result (the existence of foliations of equilibria) is the conclusion (using KAM theory) of several recent papers. Hence, we obtain that the KAM solutions recently established are minimizers when the interaction is ferromagnetic and transitive (these concepts are defined later).

  10. Ternary (liquid + liquid) equilibria of {trifluorotris(perfluoroethyl)phosphate based ionic liquids + thiophene + heptane}

    International Nuclear Information System (INIS)

    Marciniak, Andrzej; Królikowski, Marek

    2012-01-01

    Highlights: ► Ternary (liquid + liquid) equilibria for 3 ionic liquid + thiophene + heptane systems. ► The influence of ionic liquid structure on phase diagrams is discussed. ► High selectivity for separation of heptane/thiophene is observed. - Abstract: Ternary (liquid + liquid) equilibria for three systems containing ionic liquids {(4-(2-methoxyethyl)-4-methylmorpholinium trifluorotris(perfluoroethyl)phosphate, 1-(2-methoxyethyl)-1-methylpiperidinium trifluorotris(perfluoroethyl)phosphate, 1-(2-methoxyethyl)-1-methylpyrrolidinium trifluorotris(perfluoroethyl)phosphate) + thiophene + heptane} have been determined at T = 298.15 K. All systems showed high solubility of thiophene in the ionic liquid and low solubility of heptane. The solute distribution coefficient and the selectivity were calculated for all systems. High values of selectivity were obtained. The experimental results have been correlated using NRTL model. The influence of ionic liquid structure on phase equilibria is discussed.

  11. Lagrangian relative equilibria for a gyrostat in the three-body problem: bifurcations and stability

    Energy Technology Data Exchange (ETDEWEB)

    Guirao, Juan L G; Vera, Juan A, E-mail: juan.garcia@upct.e, E-mail: juanantonio.vera@upct.e [Departamento de Matematica Aplicada y EstadIstica, Universidad Politecnica de Cartagena, Hospital de Marina, 30203 Cartagena, Region de Murcia (Spain)

    2010-05-14

    In this paper we consider the non-canonical Hamiltonian dynamics of a gyrostat in the frame of the three-body problem. Using geometric/mechanic methods we study the approximate dynamics of the truncated Legendre series representation of the potential of an arbitrary order. Working in the reduced problem, we study the existence of relative equilibria that we refer to as Lagrange type following the analogy with the standard techniques. We provide necessary and sufficient conditions for the linear stability of Lagrangian relative equilibria if the gyrostat morphology form is close to a sphere. Thus, we generalize the classical results on equilibria of the three-body problem and many results on them obtained by the classic approach for the case of rigid bodies.

  12. Some axisymmetric equilibria for certain ideal and resistive magnetohydrodynamics with incompressible flows

    Directory of Open Access Journals (Sweden)

    S.M. Moawad

    Full Text Available In this paper, the equilibrium properties of some ideal and resistive magnetohydrodynamics (MHD are investigated. The governing equations are taken in the steady state for parallel and non-parallel flow to magnetic filed. The governing equations are reduced to Bernoulli-Grad-Shafranov system. The problem of finding exact equilibria to the governing equations in the presence of incompressible mass flows is studied. Several nonlinear equilibria of the governing equations are obtained with aid of constructed constraints. The obtained results cover several previously configurations and include new considerations about the nonlinearity of magnetic flux stream variables. The possibility of applying the obtained results to magnetic confinement devices are discussed. Keywords: Magnetohydrodynamics, Axisymmetric plasma, Resistivity, Incompressible flows, Exact equilibria, Magnetic confinement devices

  13. A note on relative equilibria in a rotating shallow water layer

    KAUST Repository

    Ait Abderrahmane, Hamid

    2013-05-08

    Relative equilibria of two and three satellite vortices in a rotating shallow water layer have been recorded via particle image velocimetry (PIV) and their autorotation speed was estimated. This study shows that these equilibria retain the fundamental characteristics of Kelvin\\'s equilibria, and could be adequately described by the classical idealized point vortex theory. The same conclusion can also be inferred using the experimental dataset of Bergmann et al. (J. Fluid Mech., vol. 679, 2011, pp. 415-431; J. Fluid Mech., vol. 691, 2012, pp. 605-606) if the assigned field\\'s contribution to pattern rotation is included. © 2013 Cambridge University Press.

  14. Development and testing of a new apparatus for the measurement of high-pressure low-temperature phase equilibria

    DEFF Research Database (Denmark)

    Fonseca, José M.S.; von Solms, Nicolas

    2012-01-01

    A new apparatus for the study of high-pressure phase equilibria at low temperatures using an analytical method was designed, assembled and tested. The apparatus was specially developed for the study of multi-phase equilibria in systems containing hydrocarbons, water and hydrate inhibitors, at tem...

  15. Stability of the n = 1 internal kink mode in equilibria with flows

    International Nuclear Information System (INIS)

    Aydemir, A.Y.; Waelbroeck, F.L.

    1996-01-01

    Stabilizing influence of mass flows, either directly or through their shearing action, on various modes is now generally recognized. Here we examine linear and nonlinear stability of the n = 1 internal kink mode in equilibria with toroidal rotation, using our nonlinear, initial-value MHD code CTD, which can be used to generate self-consistent equilibria with flows in arbitrary geometries. It is well known that equilibrium mass flows introduce complications in determination of MHD equilibria and their stability properties, such as the loss of self-adjointness and an increase in the number of conditions required to uniquely determine the equilibria. Thus, even with purely toroidal flows, an implicit statement about the equation of state is needed, in addition to a knowledge of the magnetic field and velocity profiles; rotation in an adiabatic plasma leads to a different equilibrium than, for example, in an isothermal one, with possibly quite different stability properties. We find that the expected stabilizing influence of toroidal rotation on n = 1 is generally absent in adiabatically generated equilibria in which, of all the relevant thermodynamic variables, only the specific entropy is a flux function, s = s (ψ). Fortunately, physically more relevant isothermal case where the temperature is constant on flux surfaces, T = T(ψ), has more favorable stability characteristics. On the other hand, an inconsistent but common practice of ignoring density perturbations, a benign omission for static equilibria, leads to overly optimistic results when equilibrium flows axe present, predicting stability when there may not be any. The crucial role played by the equation of state in determining equilibrium raises questions regarding the role of parallel transport in stability calculations; this and other nonideal effects, along with the role of plasma β vs. the rotational β, and nonlinear stability when the mode is pushed beyond marginality, will be discussed

  16. Existence of three-dimensional ideal-magnetohydrodynamic equilibria with current sheets

    Energy Technology Data Exchange (ETDEWEB)

    Loizu, J. [Max-Planck-Institut für Plasmaphysik, D-17491 Greifswald (Germany); Princeton Plasma Physics Laboratory, PO Box 451, Princeton, New Jersey 08543 (United States); Hudson, S. R.; Bhattacharjee, A.; Lazerson, S. [Princeton Plasma Physics Laboratory, PO Box 451, Princeton, New Jersey 08543 (United States); Helander, P. [Max-Planck-Institut für Plasmaphysik, D-17491 Greifswald (Germany)

    2015-09-15

    We consider the linear and nonlinear ideal plasma response to a boundary perturbation in a screw pinch. We demonstrate that three-dimensional, ideal-MHD equilibria with continuously nested flux-surfaces and with discontinuous rotational-transform across the resonant rational-surfaces are well defined and can be computed both perturbatively and using fully nonlinear equilibrium calculations. This rescues the possibility of constructing MHD equilibria with current sheets and continuous, smooth pressure profiles. The results predict that, even if the plasma acts as a perfectly conducting fluid, a resonant magnetic perturbation can penetrate all the way into the center of a tokamak without being shielded at the resonant surface.

  17. Nash equilibria in quantum games with generalized two-parameter strategies

    International Nuclear Information System (INIS)

    Flitney, Adrian P.; Hollenberg, Lloyd C.L.

    2007-01-01

    In the Eisert protocol for 2x2 quantum games [J. Eisert, et al., Phys. Rev. Lett. 83 (1999) 3077], a number of authors have investigated the features arising from making the strategic space a two-parameter subset of single qubit unitary operators. We argue that the new Nash equilibria and the classical-quantum transitions that occur are simply an artifact of the particular strategy space chosen. By choosing a different, but equally plausible, two-parameter strategic space we show that different Nash equilibria with different classical-quantum transitions can arise. We generalize the two-parameter strategies and also consider these strategies in a multiplayer setting

  18. Tokamak equilibria with non-parallel flow in a triangularity-deformed axisymmetric toroidal coordinate system

    Directory of Open Access Journals (Sweden)

    Ap Kuiroukidis

    2018-01-01

    Full Text Available We consider a generalized Grad–Shafranov equation (GGSE in a triangularity-deformed axisymmetric toroidal coordinate system and solve it numerically for the generic case of ITER-like and JET-like equilibria with non-parallel flow. It turns out that increase of the triangularity improves confinement by leading to larger values of the toroidal beta and the safety factor. This result is supported by the application of a criterion for linear stability valid for equilibria with flow parallel to the magnetic field. Also, the parallel flow has a weaker stabilizing effect.

  19. Exotic equilibria of Harary graphs and a new minimum degree lower bound for synchronization

    KAUST Repository

    Canale, Eduardo A.

    2015-02-01

    © 2015 AIP Publishing LLC. This work is concerned with stability of equilibria in the homogeneous (equal frequencies) Kuramoto model of weakly coupled oscillators. In 2012 [R. Taylor, J. Phys. A: Math. Theor. 45, 1-15 (2012)], a sufficient condition for almost global synchronization was found in terms of the minimum degree-order ratio of the graph. In this work, a new lower bound for this ratio is given. The improvement is achieved by a concrete infinite sequence of regular graphs. Besides, non standard unstable equilibria of the graphs studied in Wiley et al. [Chaos 16, 015103 (2006)] are shown to exist as conjectured in that work.

  20. Peptide models of protein metastable binding sites: competitive kinetics of isomerization and hydrolysis.

    Science.gov (United States)

    Khan, S A; Sekulski, J M; Erickson, B W

    1986-09-09

    alpha 2-Macroglobulin and the complement components C3 and C4 each contain a metastable binding site that is essential for covalent attachment. Two cyclic peptides are useful models of these unusual protein sites. Five-membered lactam 1 (CH3CO-Gly-Cys-Gly-Glu-Glp-Asn-NH2) contains an internal residue of pyroglutamic acid (Glp). Fifteen-membered thiolactone 2 (CH3CO-Gly-Cys-Gly-Glu-Glu-Asn-NH2 15-thiolactone) contains a thiol ester bond between Cys-2 and Glu-5. These isomeric hexapeptides are spontaneously interconverted in water. Competing with the two isomerization reactions are three reactions involving hydrolysis of 1 and 2. These five processes were found to occur simultaneously under physiologic conditions (phosphate-buffered saline, pH 7.3, 37 degrees C). Best estimates of the five rate constants for these apparent first-order reactions were obtained by comparing the observed molar percentages of peptides 1-4 with those calculated from a set of exponential equations. Both isomerization reactions (ring expansion of 1 to 2, k1 = 6.4 X 10(-5) s-1; ring contraction of 2 to 1, k-1 = 69 X 10(-5) s-1) proceeded faster than any of the hydrolysis reactions: alpha-cleavage of 1 with fragmentation to form dipeptide 3 (k2 = 3.3 X 10(-5) s-1), gamma-cleavage of 1 with ring opening to yield mercapto acid 4 (k3 = 0.35 X 10(-5) s-1), and hydrolysis of 2 with ring opening to give 4 (k4 = 1.9 X 10(-5) s-1). The isomerization rate ratio (k1/k-1 = 10.9) agreed with the isomer ratio at equilibrium (1:2 = 11 starting from 1 and 10 starting from 2). The alpha/gamma regioselectivity ratio (k2/k3 = 9.7) for hydrolysis of the internal Glp residue of 1 was consistent with results for model tripeptides. Part of the chemistry of the protein metastable binding sites can be explained by similar isomerization and hydrolysis reactions.

  1. K isomerism and collectivity in neutron-rich rare-earth isotopes

    Science.gov (United States)

    Patel, Zena

    Neutron-rich rare-earth isotopes were produced by in-flight fission of 238U ions at the Radioactive Isotope Beam Factory (RIBF), RIKEN, Japan. In-flight fission of a heavy, high-intensity beam of 238U ions on a light target provides the cleanest secondary beams of neutron-rich nuclei in the rare-earth region of isotopes. In-flight fission is advantageous over other methods of nuclear production, as it allows for a secondary beam to be extracted, from which the beam species can be separated and identified. The excited states of nuclei are studied by delayed isomeric or beta-delayed gamma-ray spectroscopy. New K isomers were found in Sm (Z=62), Eu (Z=63), and Gd (Z=64) isotopes. The key results are discussed here. Excited states in the N=102 isotones 166Gd and 164Sm have been observed following isomeric decay for the first time. The K-isomeric states in 166Gd and 164Sm are due to 2-quasiparticle configurations. Based on the decay patterns and potential energy surface calculations, including beta6 deformation, both isomers are assigned a (6-) spin-parity. The half-lives of the isomeric states have been measured to be 950(60)ns and 600(140)ns for 166Gd and 164Sm respectively. Collective observables are discussed in light of the systematics of the region, giving insight into nuclear shape evolution. The decrease in the ground state band energies of 166Gd and 164Sm (N=102) compared to 164Gd and 162Sm (N=100) respectively, presents evidence for the predicted deformed shell closure at N=100. A 4-quasiparticle isomeric state has been discovered in 160Sm: the lightest deformed nucleus with a 4-quasiparticle isomer to date. The isomeric state is assigned an (11+) spin-parity with a measured half-life of 1.8(4)us. The (11+) isomeric state decays into a rotational band structure, based on a (6-) v5/2-[523] ⊗ v7/2+[633] bandhead, determined from the extracted gK-gR values. Potential energy surface and blocked BCS calculations were performed in the deformed midshell region

  2. Phase Equilibria and Compressibility of bastnaesite-(La)

    Science.gov (United States)

    Rowland, R. L., II; Burnley, P. C.

    2015-12-01

    Bastnaesite (Ce,La,Y)CO3(F,OH) is a rare earth element (REE) bearing ore mineral. REEs are more common in the Earth's crust than precious metals like gold or platinum, but are not commonly concentrated in economically viable ore deposits. For over a decade, China has been the world's leading supplier of REEs. Recent export restrictions from China have necessitated the search for new deposits. Determining basic material properties such as phase equilibria and the equation of state for bastnaesite helps in understanding the processes that form REE ore deposits and thereby assist in locating new deposits. For this study we focus on the lanthanum-fluoride variant of bastnaesite (LaCO3F) since it can be easily synthesized in the laboratory. Previous work by others determined that in both open and closed systems at atmospheric pressure bastnaesite decomposes to lanthanum oxyfluoride and carbon dioxide (LaOF + CO2) above 325°C; at 100 MPa bastnaesite decomposes above 860°C (Hsu, 1992). Using a Griggs-type modified piston cylinder apparatus, we pressurized samples of synthetic bastnaesite-(La) to conditions ranging from 250 MPa to 1.2 GPa, and then subjected each sample to constant temperatures ranging from 700°C to 1050°C for a minimum of five hours. We then analyzed the samples with X-ray powder diffraction to identify phases present and determined that bastnaesite-(La) is stable at 250 MPa up to approximately 800°C and at 1.0 GPa up to approximately 900°C. Reversal experiments are underway. In order to develop an equation of state for bastnaesite-(La), we studied single crystals via monochromatic synchrotron X-ray diffraction in the diamond anvil cell at HPCAT (Sector 16), Advanced Photon Source (APS), Argonne National Laboratory. Measurements were made at pressures ranging from ambient to nearly 4 GPa. From these diffraction patterns, we determine the structure of bastnaesite-(La), and the change in unit cell volume as a function of pressure can be fit to a Birch

  3. Phase equilibria constraints on models of subduction zone magmatism

    Science.gov (United States)

    Myers, James D.; Johnston, Dana A.

    Petrologic models of subduction zone magmatism can be grouped into three broad classes: (1) predominantly slab-derived, (2) mainly mantle-derived, and (3) multi-source. Slab-derived models assume high-alumina basalt (HAB) approximates primary magma and is derived by partial fusion of the subducting slab. Such melts must, therefore, be saturated with some combination of eclogite phases, e.g. cpx, garnet, qtz, at the pressures, temperatures and water contents of magma generation. In contrast, mantle-dominated models suggest partial melting of the mantle wedge produces primary high-magnesia basalts (HMB) which fractionate to yield derivative HAB magmas. In this context, HMB melts should be saturated with a combination of peridotite phases, i.e. ol, cpx and opx, and have liquid-lines-of-descent that produce high-alumina basalts. HAB generated in this manner must be saturated with a mafic phase assemblage at the intensive conditions of fractionation. Multi-source models combine slab and mantle components in varying proportions to generate the four main lava types (HMB, HAB, high-magnesia andesites (HMA) and evolved lavas) characteristic of subduction zones. The mechanism of mass transfer from slab to wedge as well as the nature and fate of primary magmas vary considerably among these models. Because of their complexity, these models imply a wide range of phase equilibria. Although the experiments conducted on calc-alkaline lavas are limited, they place the following limitations on arc petrologic models: (1) HAB cannot be derived from HMB by crystal fractionation at the intensive conditions thus far investigated, (2) HAB could be produced by anhydrous partial fusion of eclogite at high pressure, (3) HMB liquids can be produced by peridotite partial fusion 50-60 km above the slab-mantle interface, (4) HMA cannot be primary magmas derived by partial melting of the subducted slab, but could have formed by slab melt-peridotite interaction, and (5) many evolved calc

  4. Stability and isomerization reactions of phenyl cation C{sub 6}H{sub 5}{sup +} isomers

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Dandan [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yang, Xue [College of Science, Jilin Institute of Chemical Technology, Jilin 132022 (China); Zhang, Xiaomei; Shan, Shimin [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Xu, Haifeng, E-mail: xuhf@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China); Yan, Bing, E-mail: yanbing@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China); Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy (Jilin University), Changchun 130012 (China)

    2016-03-01

    Highlights: • A total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations were obtained at density functional theory. • The stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers were performed. • The structures, frequencies, thermodynamic properties of isomers were summarized. • Ring to ring or chain isomerization pathways were investigated using IRC method. • Result shows reactions contain hydrogen transfer, bond broken and reconstruction. - Abstract: As a key polyatomic molecular cation that plays a pivotal role in growth of the polycyclic aromatic hydrocarbons, phenyl cation C{sub 6}H{sub 5}{sup +} exhibits various isomers and isomerization reactions. Investigation on the structure and stability of the isomers as well as the isomerization is important for better understanding the chemical reactions involving C{sub 6}H{sub 5}{sup +} cations. In this work, we have performed a theoretical study on the stability and isomerization reactions of C{sub 6}H{sub 5}{sup +} isomers at density functional theory B3LYP/6-311G (d, p) level. We have obtained a total of 60 isomers of C{sub 6}H{sub 5}{sup +} cations, most of which are reported for the first time. The geometries, vibrational frequencies, thermodynamic properties and stability of 28 out of 60 isomers have been summarized in detail. Different ring-to-ring and ring-to-chain isomerization pathways, which are connected via 28 transition states, have been investigated using the intrinsic reaction coordinate method. The results show that the isomerization reactions occur via hydrogen migration followed by bond-breaking and reconstruction.

  5. Modelling of phase equilibria of glycol ethers mixtures using an association model

    DEFF Research Database (Denmark)

    Garrido, Nuno M.; Folas, Georgios; Kontogeorgis, Georgios

    2008-01-01

    Vapor-liquid and liquid-liquid equilibria of glycol ethers (surfactant) mixtures with hydrocarbons, polar compounds and water are calculated using an association model, the Cubic-Plus-Association Equation of State. Parameters are estimated for several non-ionic surfactants of the polyoxyethylene ...

  6. Using a Differential Scanning Calorimeter to Teach Phase Equilibria to Students of Igneous and Metamorphic Petrology

    Science.gov (United States)

    Maria, Anton H.; Millam, Evan L.; Wright, Carrie L.

    2011-01-01

    As an aid for teaching phase equilibria to undergraduate students of igneous and metamorphic petrology, we have designed a laboratory exercise that allows them to create a phase diagram from data produced by differential scanning calorimetry. By preparing and analyzing samples of naphthalene and phenanthrene, students acquire hands-on insight into…

  7. A Computer Algebra Approach to Solving Chemical Equilibria in General Chemistry

    Science.gov (United States)

    Kalainoff, Melinda; Lachance, Russ; Riegner, Dawn; Biaglow, Andrew

    2012-01-01

    In this article, we report on a semester-long study of the incorporation into our general chemistry course, of advanced algebraic and computer algebra techniques for solving chemical equilibrium problems. The method presented here is an alternative to the commonly used concentration table method for describing chemical equilibria in general…

  8. Geostrophic tripolar vortices in a two-layer fluid: Linear stability and nonlinear evolution of equilibria

    Science.gov (United States)

    Reinaud, J. N.; Sokolovskiy, M. A.; Carton, X.

    2017-03-01

    We investigate equilibrium solutions for tripolar vortices in a two-layer quasi-geostrophic flow. Two of the vortices are like-signed and lie in one layer. An opposite-signed vortex lies in the other layer. The families of equilibria can be spanned by the distance (called separation) between the two like-signed vortices. Two equilibrium configurations are possible when the opposite-signed vortex lies between the two other vortices. In the first configuration (called ordinary roundabout), the opposite signed vortex is equidistant to the two other vortices. In the second configuration (eccentric roundabouts), the distances are unequal. We determine the equilibria numerically and describe their characteristics for various internal deformation radii. The two branches of equilibria can co-exist and intersect for small deformation radii. Then, the eccentric roundabouts are stable while unstable ordinary roundabouts can be found. Indeed, ordinary roundabouts exist at smaller separations than eccentric roundabouts do, thus inducing stronger vortex interactions. However, for larger deformation radii, eccentric roundabouts can also be unstable. Then, the two branches of equilibria do not cross. The branch of eccentric roundabouts only exists for large separations. Near the end of the branch of eccentric roundabouts (at the smallest separation), one of the like-signed vortices exhibits a sharp inner corner where instabilities can be triggered. Finally, we investigate the nonlinear evolution of a few selected cases of tripoles.

  9. A numerical algorithm to find all feedback Nash equilibria in scalar affine quadratic differential games

    NARCIS (Netherlands)

    Engwerda, Jacob

    2015-01-01

    This note deals with solving scalar coupled algebraic Riccati equations. These equations arise in finding linear feedback Nash equilibria of the scalar N-player affine quadratic differential game. A numerical procedure is provided to compute all the stabilizing solutions. The main idea is to

  10. Thermodynamic modelling of phase equilibria in Al–Ga–P–As system

    Indian Academy of Sciences (India)

    A generalized thermodynamic expression of the liquid Al–Ga–P–As alloys is used in conjunction with the solid solution model in determining the solid–liquid equilibria at 1173 K and 1273 K. The liquid solution model contains thirtyseven parameters. Twentyfour of them pertain to those of the six constituent binaries, twelve ...

  11. Ternary liquid-liquid equilibria for mixtures of toluene + n-heptane + an ionic liquid

    NARCIS (Netherlands)

    Meindersma, G.W.; Podt, J.G.; de Haan, A.B.

    2006-01-01

    This research has been focused on a study of sulfolane and four ionic liquids as solvents in liquid–liquid extraction. Liquid–liquid equilibria data were obtained for mixtures of (sulfolane or 4-methyl-N-butylpyridinium tetrafluoroborate ([mebupy]BF4) or 1-ethyl-3-methylimidazolium ethylsulfate

  12. Construction of Subgame-Perfect Mixed Strategy Equilibria in Repeated Games

    NARCIS (Netherlands)

    Berg, Kimmo; Schoenmakers, Gijsbertus

    2017-01-01

    This paper examines how to construct subgame-perfect mixed-strategy equilibria in discounted repeated games with perfect monitoring.We introduce a relatively simple class of strategy profiles that are easy to compute and may give rise to a large set of equilibrium payoffs. These sets are called

  13. On pure-strategy Nash equilibria in price-quantity games

    NARCIS (Netherlands)

    Bos, I.; Vermeulen, A.J.

    2015-01-01

    This paper examines the existence and characteristics of pure-strategy Nash equilibria in oligopoly models in which firms set both prices and quantities. Existence is proved for a broad and natural class of price-quantity games. With differentiated products, the equilibrium outcome is similar to

  14. The effects of risk preferences in mixed-strategy equilibria of 2x2 games

    Czech Academy of Sciences Publication Activity Database

    Engelmann, D.; Steiner, Jakub

    2007-01-01

    Roč. 60, č. 2 (2007), s. 381-388 ISSN 0899-8256 R&D Projects: GA MŠk LC542 Institutional research plan: CEZ:AV0Z70850503 Keywords : risk preferences * mixed strategy equilibria Subject RIV: AH - Economics Impact factor: 1.468, year: 2007

  15. Assessment of solid/liquid equilibria in the (U, Zr)O

    NARCIS (Netherlands)

    Mastromarino, S.; Seibert, AF; Hashem, E.; Ciccioli, A.; Prieur, Damien; Scheinost, Andreas C.; Stohr, S.; Lajarge, P; Boshoven, JG; Robba, D.; Ernstberger, M; Bottomley, D.; Manara, D

    2017-01-01

    Solid/liquid equilibria in the system UO2–ZrO2 are revisited in this work by laser heating coupled with fast optical thermometry. Phase transition points newly measured under inert gas are in fair agreement with the early measurements performed by Wisnyi et al., in 1957, the

  16. Exotic equilibria of Harary graphs and a new minimum degree lower bound for synchronization

    KAUST Repository

    Canale, Eduardo A.; Monzó n, Pablo

    2015-01-01

    © 2015 AIP Publishing LLC. This work is concerned with stability of equilibria in the homogeneous (equal frequencies) Kuramoto model of weakly coupled oscillators. In 2012 [R. Taylor, J. Phys. A: Math. Theor. 45, 1-15 (2012)], a sufficient condition

  17. Equilibria of the three-body problem with rigid dumb-bell satellite

    International Nuclear Information System (INIS)

    Elipe, A.; Palacios, M.; Pretka-Ziomek, H.

    2008-01-01

    This paper is concerned with the orbital-rotational motion of an asymmetric dumb-bell (two masses with fixed distance among them) under the attraction of a central body. For this model, we find some equilibria and give sufficient conditions for their stability

  18. Fac–mer equilibria of coordinated iminodiacetate (ida ) in ternary Cu ...

    Indian Academy of Sciences (India)

    Unknown

    Keywords. Fac–mer equilibria; CuII-iminodiacetate-imidazole/benzimidazole ternary complexes; stability constants. 1. Introduction. Mixed ligand complexes of transition metal ions with amino acids, peptides or their derivatives or analogues, and heterocyclic N-bases can serve as model compounds of bioinorganic interests ...

  19. A note on relative equilibria in a rotating shallow water layer

    KAUST Repository

    Ait Abderrahmane, Hamid; Fayed, Mohamed; Ng, Hoidick; Vatistas, Georgios H.

    2013-01-01

    the fundamental characteristics of Kelvin's equilibria, and could be adequately described by the classical idealized point vortex theory. The same conclusion can also be inferred using the experimental dataset of Bergmann et al. (J. Fluid Mech., vol. 679, 2011

  20. Systematic identification method for data analysis and phase equilibria modelling for lipids systems

    DEFF Research Database (Denmark)

    Perederic, Olivia A.; Cunico, Larissa P.; Kalakul, Sawitree

    2018-01-01

    Industrial use of lipids has been increasing as a consequence of increased developments related to biobased economies. In addition to applications in food-products, lipids are used by many industrial sectors, for example, biodiesel, edible oil, health, and personal care. Phase equilibria...

  1. Helical equilibria and criteria for the kink instability of cylindrical tokamak

    International Nuclear Information System (INIS)

    Inoue, Sanae; Itoh, Kimitaka; Yoshikawa, Shoichi.

    1974-10-01

    Helical equilibria and criteria for the kink instability have been obtained numerically for various current distribution, including camel hump distribution. It is found that the unstable region expressed by q(a) is the largest in the case of uniform current. (auth.)

  2. Simulation of the high-pressure phase equilibria of hydrocarbon-water/brine systems

    DEFF Research Database (Denmark)

    Zuo, You-Xiang; Stenby, Erling Halfdan; Guo, Tian-Min

    1996-01-01

    The major objectives of this work are: (1) extend the modified Patel-Teja (MPT) equation of state proposed for aqueous electrolyte systems (Zuo and Guo, 1991) to describe the liquid-liquid and vapor-liquid-liquid equilibria of hydrocarbon-water/brine systems through introducing an unconventional...

  3. Analysis of rotation-vibration relative equilibria on the example of a tetrahedral four atom molecule

    NARCIS (Netherlands)

    Efstathiou, K; Sadovskii, DA; Zhilinskii, BI

    2004-01-01

    We study relative equilibria ( RE) of a nonrigid molecule, which vibrates about a well-defined equilibrium configuration and rotates as a whole. Our analysis unifies the theory of rotational and vibrational RE. We rely on the detailed study of the symmetry group action on the initial and reduced

  4. Theory of Perturbed Equilibria for Solving the Grad-Shafranov Equation

    International Nuclear Information System (INIS)

    Pletzer, A.; Zakharov, L.E.

    1999-01-01

    The theory of perturbed magnetohydrodynamic equilibria is presented for different formulations of the tokamak equilibrium problem. For numerical codes, it gives an explicit Newton scheme for solving the Grad-Shafranov equation subject to different constraints. The problem of stability of axisymmetric modes is shown to be a particular case of the equilibrium perturbation theory

  5. Fusion burn equilibria sensitive to the ratio between energy and helium transport

    NARCIS (Netherlands)

    Jakobs, M.A.; Lopes Cardozo, N.J.; Jaspers, R.J.E.

    2014-01-01

    An analysis of the burn equilibria of fusion reactors of the tokamak family is presented. The global (zero-dimensional) analysis is self-consistent in that it takes into account the dependence of the energy confinement on the variables of the burning plasma, such as temperature and density.

  6. New investigation of phase equilibria in the system Al-Cu-Si.

    Science.gov (United States)

    Ponweiser, Norbert; Richter, Klaus W

    2012-01-25

    The phase equilibria and invariant reactions in the system Al-Cu-Si were investigated by a combination of optical microscopy, powder X-ray diffraction (XRD), differential thermal analysis (DTA) and electron probe micro analysis (EPMA). Isothermal phase equilibria were investigated within two isothermal sections. The isothermal section at 500 °C covers the whole ternary composition range and largely confirms the findings of previous phase diagram investigations. The isothermal section at 700 °C describes phase equilibria only in the complex Cu-rich part of the phase diagram. A new ternary compound τ was found in the region between (Al,Cu)-γ(1) and (Cu,Si)-γ and its solubility range was determined. The solubility of Al in κ-CuSi was found to be extremely high at 700 °C. In contrast, no ternary solubility in the β-phase of Cu-Al was found, although this phase is supposed to form a complete solid solution according to previous phase diagram assessments. Two isopleths, at 10 and 40 at.% Si, were investigated by means of DTA and a partial ternary reaction scheme (Scheil diagram) was constructed, based on the current work and the latest findings in the binary systems Al-Cu and Cu-Si. The current study shows that the high temperature equilibria in the Cu-rich corner are still poorly understood and additional studies in this area would be favorable.

  7. A note on the energy of relative equilibria of point vortices

    DEFF Research Database (Denmark)

    Aref, Hassan

    2007-01-01

    Analytical formulas are derived for the energy of simple relative equilibria of identical point vortices such as the regular polygons, both open and centered, and the various known configurations consisting of nested regular polygons with or without a vortex at the center. ©2007 American Institute...

  8. Effect of temperature on acid–base equilibria in separation techniques. A review

    International Nuclear Information System (INIS)

    Gagliardi, Leonardo G.; Tascon, Marcos; Castells, Cecilia B.

    2015-01-01

    Studies on the theoretical principles of acid–base equilibria are reviewed and the influence of temperature on secondary chemical equilibria within the context of separation techniques, in water and also in aqueous-organic solvent mixtures, is discussed. In order to define the relationships between the retention in liquid chromatography or the migration velocity in capillary electrophoresis and temperature, the main properties of acid–base equilibria have to be taken into account for both, the analytes and the conjugate pairs chosen to control the solution pH. The focus of this review is based on liquid–liquid extraction (LLE), liquid chromatography (LC) and capillary electrophoresis (CE), with emphasis on the use of temperature as a useful variable to modify selectivity on a predictable basis. Simplified models were evaluated to achieve practical optimizations involving pH and temperature (in LLE and CE) as well as solvent composition in reversed-phase LC. - Highlights: • The study of theoretical principles of acid–base equilibrium has been reviewed. • The proton transfer process is often present in the analytical separation practice. • The influence of temperature on secondary chemical equilibria is examined. • The focus is laid on liquid chromatography and capillary electrophoresis. • Temperature can be a useful variable to modify selectivity under predictable basis

  9. Prediction of Pure Component Adsorption Equilibria Using an Adsorption Isotherm Equation Based on Vacancy Solution Theory

    DEFF Research Database (Denmark)

    Marcussen, Lis; Aasberg-Petersen, K.; Krøll, Annette Elisabeth

    2000-01-01

    An adsorption isotherm equation for nonideal pure component adsorption based on vacancy solution theory and the Non-Random-Two-Liquid (NRTL) equation is found to be useful for predicting pure component adsorption equilibria at a variety of conditions. The isotherm equation is evaluated successfully...... adsorption systems, spreading pressure and isosteric heat of adsorption are also calculated....

  10. The SX Solver: A New Computer Program for Analyzing Solvent-Extraction Equilibria

    International Nuclear Information System (INIS)

    McNamara, B.K.; Rapko, B.M.; Lumetta, G.J.

    1999-01-01

    A new computer program, the SX Solver, has been developed to analyze solvent-extraction equilibria. The program operates out of Microsoft Excel and uses the built-in ''Solver'' function to minimize the sum of the square of the residuals between measured and calculated distribution coefficients. The extraction of nitric acid by tributylphosphate has been modeled to illustrate the program's use

  11. The SX Solver: A Computer Program for Analyzing Solvent-Extraction Equilibria: Version 3.0

    International Nuclear Information System (INIS)

    Lumetta, Gregg J.

    2001-01-01

    A new computer program, the SX Solver, has been developed to analyze solvent-extraction equilibria. The program operates out of Microsoft Excel and uses the built-in Solver function to minimize the sum of the square of the residuals between measured and calculated distribution coefficients. The extraction of nitric acid by tributyl phosphate has been modeled to illustrate the programs use

  12. Control Algorithms Along Relative Equilibria of Underactuated Lagrangian Systems on Lie Groups

    DEFF Research Database (Denmark)

    Nordkvist, Nikolaj; Bullo, F.

    2008-01-01

    We present novel algorithms to control underactuated mechanical systems. For a class of invariant systems on Lie groups, we design iterative small-amplitude control forces to accelerate along, decelerate along, and stabilize relative equilibria. The technical approach is based upon a perturbation...

  13. Control algorithms along relative equilibria of underactuated Lagrangian systems on Lie groups

    DEFF Research Database (Denmark)

    Nordkvist, Nikolaj; Bullo, Francesco

    2007-01-01

    We present novel algorithms to control underactuated mechanical systems. For a class of invariant systems on Lie groups, we design iterative small-amplitude control forces to accelerate along, decelerate along, and stabilize relative equilibria. The technical approach is based upon a perturbation...

  14. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

    2018-01-16

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

  15. A system to measure isomeric state half-lives in the 10 ns to 10 μs range

    Energy Technology Data Exchange (ETDEWEB)

    Toufen, D. L., E-mail: dennis@if.usp.br [Institute of Physics, University of São Paulo, C.P. 66318, 05315-970 São Paulo, São Paulo (Brazil); Federal Institute of Education, Science and Technology of São Paulo - IFSP, 07115-000 Guarulhos, São Paulo (Brazil); Allegro, P. R. P.; Medina, N. H.; Oliveira, J. R. B.; Cybulska, E. W.; Seale, W. A.; Ribas, R. V. [Institute of Physics, University of São Paulo, C.P. 66318, 05315-970 São Paulo, São Paulo (Brazil); Linares, R. [Fluminense Federal University, 24220-900 Niterói, Rio de Janeiro (Brazil); Silveira, M. A. G. [Universitary Center of FEI, 09850-901 São Bernardo do Campo, São Paulo (Brazil)

    2014-07-15

    The Isomeric State Measurement System (SISMEI) was developed to search for isomeric nuclear states produced by fusion-evaporation reactions. The SISMEI consists of 10 plastic phoswich telescopes, two lead shields, one NaI(Tl) scintillation detector, two Compton suppressed HPGe γ-ray detectors, and a cone with a recoil product catcher. The new system was tested at the 8 UD Pelletron tandem accelerator of the University of São Paulo with the measurement of two known isomeric states: {sup 54}Fe, 10{sup +} state (E = 6527.1 (11) keV, T{sub 1/2} = 364(7) ns) and the 5/2{sup +} state of {sup 19}F (E = 197.143 (4) keV, T{sub 1/2} = 89.3 (10) ns). The results indicate that the system is capable of identifying delayed transitions, of measuring isomeric state lifetimes, and of identifying the feeding transitions of the isomeric state through the delayed γ-γ coincidence method. The measured half-life for the 10{sup +} state was T{sub 1/2} = 365(14) ns and for the 5/2{sup +} state, 100(36) ns.

  16. A system to measure isomeric state half-lives in the 10 ns to 10 μs range

    Science.gov (United States)

    Toufen, D. L.; Allegro, P. R. P.; Medina, N. H.; Oliveira, J. R. B.; Cybulska, E. W.; Seale, W. A.; Linares, R.; Silveira, M. A. G.; Ribas, R. V.

    2014-07-01

    The Isomeric State Measurement System (SISMEI) was developed to search for isomeric nuclear states produced by fusion-evaporation reactions. The SISMEI consists of 10 plastic phoswich telescopes, two lead shields, one NaI(Tl) scintillation detector, two Compton suppressed HPGe γ-ray detectors, and a cone with a recoil product catcher. The new system was tested at the 8 UD Pelletron tandem accelerator of the University of São Paulo with the measurement of two known isomeric states: 54Fe, 10+ state (E = 6527.1 (11) keV, T1/2 = 364(7) ns) and the 5/2+ state of 19F (E = 197.143 (4) keV, T1/2 = 89.3 (10) ns). The results indicate that the system is capable of identifying delayed transitions, of measuring isomeric state lifetimes, and of identifying the feeding transitions of the isomeric state through the delayed γ-γ coincidence method. The measured half-life for the 10+ state was T1/2 = 365(14) ns and for the 5/2+ state, 100(36) ns.

  17. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

    2018-01-01

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

  18. A comprehensive mechanistic picture of the isomerizing alkoxycarbonylation of plant oils

    KAUST Repository

    Roesle, Philipp

    2014-12-03

    Theoretical studies on the overall catalytic cycle of isomerizing alkoxycarbonylation reveal the steric congestion around the diphosphine coordinated Pd-center as decisive for selectivity and productivity. The energy profile of isomerization is flat with diphosphines of variable steric bulk, but the preference for the formation of the linear Pd-alkyl species is more pronounced with sterically demanding diphosphines. CO insertion is feasible and reversible for all Pd-alkyl species studied and only little affected by the diphosphine. The overall rate-limiting step associated with the highest energetic barrier is methanolysis of the Pd-acyl species. Considering methanolysis of the linear Pd-acyl species, whose energetic barrier is lowest within all the Pd-acyl species studied, the barrier is calculated to be lower for more congesting diphosphines. Calculations indicate that energy differences of methanolysis of the linear versus branched Pd-acyls are more pronounced for more bulky diphosphines, due to involvement of different numbers of methanol molecules in the transition state. Experimental studies under pressure reactor conditions showed a faster conversion of shorter chain olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced by pressure reactor and NMR studies. Multiple unsaturated fatty acids were observed to form a terminal Pd-allyl species upon reaction with the catalytically active Pd-hydride species. This process and further carbonylation are slow compared to isomerizing methoxycarbonylation of monounsaturated fatty acids, but selective.

  19. A comprehensive mechanistic picture of the isomerizing alkoxycarbonylation of plant oils.

    Science.gov (United States)

    Roesle, Philipp; Caporaso, Lucia; Schnitte, Manuel; Goldbach, Verena; Cavallo, Luigi; Mecking, Stefan

    2014-12-03

    Theoretical studies on the overall catalytic cycle of isomerizing alkoxycarbonylation reveal the steric congestion around the diphosphine coordinated Pd-center as decisive for selectivity and productivity. The energy profile of isomerization is flat with diphosphines of variable steric bulk, but the preference for the formation of the linear Pd-alkyl species is more pronounced with sterically demanding diphosphines. CO insertion is feasible and reversible for all Pd-alkyl species studied and only little affected by the diphosphine. The overall rate-limiting step associated with the highest energetic barrier is methanolysis of the Pd-acyl species. Considering methanolysis of the linear Pd-acyl species, whose energetic barrier is lowest within all the Pd-acyl species studied, the barrier is calculated to be lower for more congesting diphosphines. Calculations indicate that energy differences of methanolysis of the linear versus branched Pd-acyls are more pronounced for more bulky diphosphines, due to involvement of different numbers of methanol molecules in the transition state. Experimental studies under pressure reactor conditions showed a faster conversion of shorter chain olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced by pressure reactor and NMR studies. Multiple unsaturated fatty acids were observed to form a terminal Pd-allyl species upon reaction with the catalytically active Pd-hydride species. This process and further carbonylation are slow compared to isomerizing methoxycarbonylation of monounsaturated fatty acids, but selective.

  20. Positionally isomeric organic gelators: structure-gelation study, racemic versus enantiomeric gelators, and solvation effects.

    Science.gov (United States)

    Caplar, Vesna; Frkanec, Leo; Sijaković Vujicić, Natasa; Zinić, Mladen

    2010-03-08

    Low molecular weight gelator molecules consisting of aliphatic acid, amino acid (phenylglycine), and omega-aminoaliphatic acid units have been designed. By varying the number of methylene units in the aliphatic and omega-aminoaliphatic acid chains, as defined by descriptors m and n, respectively, a series of positionally isomeric gelators having different positions of the peptidic hydrogen-bonding unit within the gelator molecule has been obtained. The gelation properties of the positional isomers have been determined in relation to a defined set of twenty solvents of different structure and polarity and analyzed in terms of gelator versatility (G(ver)) and effectiveness (G(eff)). The results of gelation tests have shown that simple synthetic optimizations of a "lead gelator molecule" by variation of m and n, end-group polarity (carboxylic acid versus sodium carboxylate), and stereochemistry (racemate versus optically pure form) allowed the identification of gelators with tremendously improved versatility (G(ver)) and effectiveness (G(eff)). Dramatic differences in G(eff) values of up to 70 times could be observed between pure racemate/enantiomer pairs of some gelators, which were manifested even in the gelation of very similar solvents such as isomeric xylenes. The combined results of spectroscopic ((1)H NMR, FTIR), electron microscopy (TEM), and X-ray diffraction studies suggest similar organization of the positionally isomeric gelators at the molecular level, comprising parallel beta-sheet hydrogen-bonded primary assemblies that form inversed bilayers at a higher organizational level. Differential scanning calorimetry (DSC) studies of selected enantiomer/racemate gelator pairs and their o- and p-xylene gels revealed the simultaneous presence of different polymorphs in the racemate gels. The increased gelation effectiveness of the racemate compared to that of the single enantiomer is most likely a consequence of its spontaneous resolution into enantiomeric

  1. Outcomes following the Kawashima procedure for single-ventricle palliation in left atrial isomerism.

    Science.gov (United States)

    Vollebregt, Anne; Pushparajah, Kuberan; Rizvi, Maleeha; Hoschtitzky, Andreas; Anderson, David; Austin, Conal; Tibby, Shane M; Simpson, John

    2012-03-01

    Patients with left atrial isomerism and interrupted inferior vena cava palliated with a superior cavopulmonary connection or Kawashima procedure (KP) have a high incidence of developing pulmonary arteriovenous malformations. The necessity for hepatic vein redirection (HVR) and its timing remains a controversy. We aimed to assess the clinical outcome of patients with left atrial isomerism following a KP. The main end points were death, requirement for HVR and the impact of HVR on oxygen saturation. Retrospective review of 21 patients with a diagnosis of left atrial isomerism, interruption of the inferior vena cava and single-ventricle physiology managed with a KP at a single centre between January 1990 and March 2010. Twenty-one patients had a KP, with 12 subsequently undergoing HVR. There was relatively a constant monthly decrement in the proportion of patients who were free from death or HVR up until 60 months following the KP, with a dramatic increase in the hazard after this time. The Cox proportional hazards regression model demonstrated a reduced early risk for HVR or death in patients who underwent pulmonary artery banding versus arterial shunt as the primary procedure (hazard ratio: 0.10; P = 0.01), and an increased risk with bilateral superior vena cavas (SVCs) (hazard ratio: 3.4; P = 0.04) and age at KP (hazard ratio: 1.02 per month increase in age at KP; P = 0.02). HVR mortality was relatively high with 3 of 12 patients dying in the early postoperative period with profound cyanosis. The timing of HVR after the KP did not influence the postoperative rate of increase in oxygen saturation. These findings confirm that the majority of patients who undergo a KP will require HVR. Patients who are older at the time of the KP or having an initial arterial shunt or bilateral SVCs are at higher risk of HVR or death. The relatively high mortality at HVR was characterized by severe postoperative cyanosis.

  2. Dipole-resonance assisted isomerization in the electronic ground state using few-cycle infrared pulses.

    Science.gov (United States)

    Skocek, Oliver; Uiberacker, Christoph; Jakubetz, Werner

    2011-06-30

    A computational investigation of HCN → HNC isomerization in the electronic ground state by one- and few-cycle infrared pulses is presented. Starting from a vibrationally pre-excited reagent state, isomerization yields of more than 50% are obtained using single one- to five-cycle pulses. The principal mechanism includes two steps of population transfer by dipole-resonance (DR), and hence, the success of the method is closely linked to the polarity of the system and, in particular, the stepwise change of the dipole moment from reactant to transition state and on to products. The yield drops massively if the diagonal dipole matrix elements are artificially set to zero. In detail, the mechanism includes DR-induced preparation of a delocalized vibrational wavepacket, which traverses the barrier region and is finally trapped in the product well by DR-dominated de-excitation. The excitation and de-excitation steps are triggered by pulse lobes of opposite field direction. As the number of optical cycles is increased, the leading field lobes prepare a vibrational superposition state by off-resonant ladder climbing, which is then subjected to the three steps of the principal isomerization mechanism. DR excitation is more efficient from a preformed vibrational wavepacket than from a molecular eigenstate. The entire process can be loosely described as Tannor-Kosloff-Rice type transfer mechanism on a single potential surface effected by a single pulse, individual field lobes assuming the roles of pump- and dump-pulses. Pre-excitation to a transient wavepacket can be enhanced by applying a separate, comparatively weak few-cycle prepulse, in which the prepulse prepares a vibrational wavepacket. The two-pulse setup corresponds to a double Tannor-Kosloff-Rice control scheme on a single potential surface.

  3. Abnormal radioactive decays out of long-lived super- and hyper-deformed isomeric states

    International Nuclear Information System (INIS)

    Marinov, A.; Gelberg, S.; Kolb, D.

    2000-01-01

    Complete text of publication follows. Recently (1-3) long-lived isomeric states have been found in the super- and hyper-deformed wells of the potential. These isomers manifested themselves by abnormal particle decays. An isomeric state in the superdeformed well of the potential in the parent nucleus can decay by very enhanced α-particle groups to superdeformed states in the daughter (1) or by very retarded α-particles (3) and also by protons (2) to normal states in the daughters. Similarly an isomeric state in the hyper-deformed well may decay by very retarded α-particle groups to superdeformed states (3), or by very enhanced α-groups to hyper-deformed states in the daughter nucleus (4). All these very unusual decay modes have been observed experimentally (1-4). For instance, a very high energy α-group of 8.6 MeV with 40d ≤ t 1/2 ≤ 2y (retardation factor of ∼10 13 ) has been observed in 195 Hg and interpreted as a III min → II min α-transition (3). Likewise, relatively low-energy and very enhanced α-particle groups (enhancement factors of 10 5 to 10 7 ) have been seen in several actinide sources and interpreted as due to II min → II min and III min → III min transitions (4). These unusual decay modes introduce new considerations in the study of heavy and superheavy elements. For instance, if low-energy α-particle groups around 4.4 - 4.6 MeV have been seen in nature (5), they may be interpreted as due to very enhanced III min → III min transitions in the superheavy element region around Z = 108 (eka-Os) with t 1/2 ∼10 8 y rather than ∼10 15 y as expected for normal α-transitions of such energies in this region, or due to very retarded III min → II min or II min → I min decays in nuclei around Os itself. In both cases, if such activities have been seen in nature, they indicate that the existence of the II min and III min isomeric states may be important in the nucleosynthesis process. It should be mentioned that long-lived high

  4. Cascade olefin isomerization/intramolecular Diels-Alder reaction catalyzed by N-heterocyclic carbenes.

    Science.gov (United States)

    Kowalczyk, Marcin; Lupton, David W

    2014-05-19

    The addition of an N-heterocyclic carbene to the carbonyl group of an α,β,γ,δ-unsaturated enol ester affords a hemiacetal azolium intermediate that enables a cascade olefin isomerization/Diels-Alder reaction, for which mechanistic studies implicate Lewis base catalysis. Preliminary studies into the utility of the products have been undertaken with reductive and oxidative cleavage, giving materials for potential use in complex-target synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Modelling of tracer-kinetic results using xylene isomerization as an example

    International Nuclear Information System (INIS)

    Bauer, F.J.; Dermietzel, J.; Roesseler, M.; Koch, H.

    1976-01-01

    The analysis of results from differential or/and integral reactor experiments often admits the interpretation of a chemical reaction in several ways. In addition, the use of mathematical methods for the model selection and planning of experiments is rendered more difficult by great confidence intervals of the ascertained model parameters. The application of radioactively labelled molecules results in improving the knowledge of reaction mechanisms as well as the assessment of parameters obtained. This is shown on the basis of modelling the isomerization of xylene. (author)

  6. Macrocyclic effects upon isomeric Cu M and M Cu cores. Formation ...

    Indian Academy of Sciences (India)

    Administrator

    from the iminic site to the aminic site in the synthesis of 10 is explained by ... Our previous studies suggest that isomeric MIICuII ... Calcd. for C24H27Br2ClCuN4NiO8: C 35⋅28; H 3⋅33; N 6⋅86; Cu 7⋅78; Ni .... Electronic absorption spectra in .... 3. 1497(1). 1452. ⋅3(5). 2992(1). 1860(2). 3206(1). Z. 2. 2. 4. 2. 4. D calcd. /g.

  7. Isotope exchange study of nickel xanthate in presence of aniline and isomeric toluidines

    International Nuclear Information System (INIS)

    Naidu, G.R.K.; Naidu, P.R.

    1982-01-01

    Isotopic exchange behaviour of nickel xanthate is studied in the presence of aniline and three isomeric toluidines at 18degC. The effect of base concentration is also studied on the exchange rate. The results show that the complex is labile in the kinetic sense in the presence of aniline meta and para toluidines. The rate of exchange increases with and para toluidines. The rate of exchange increases with increase in concentration of the base. The complex displays inert behaviour in the presence of o-toluidine and it is ascribed to dominant steric effect. (author)

  8. Magnetic dipole moments of High-K isomeric states in Hf isotopes

    CERN Multimedia

    Walters, W; Nishimura, K; Bingham, C R

    2007-01-01

    It is proposed to make precision measurements of the magnetic moments of 5 multi-quasi-particle K-isomers in Hf nuclei by the Nuclear Magnetic Resonance of Oriented Nuclei (NMR/ON) technique using the NICOLE on-line nuclear orientation facility and exploiting the unique HfF$_{3}$ beams recently available at ISOLDE. Results will be used to extract single-particle and collective g-factors of the isomeric states and their excitations and to shed new light on their structure.

  9. β decay and isomeric properties of neutron-rich Ca and Sc isotopes

    International Nuclear Information System (INIS)

    Crawford, H. L.; Mantica, P. F.; Berryman, J. S.; Stoker, J. B.; Janssens, R. V. F.; Carpenter, M. P.; Kay, B. P.; Lauritsen, T.; Zhu, S.; Broda, R.; Cieplicka, N.; Fornal, B.; Grinyer, G. F.; Minamisono, K.; Hoteling, N.; Stefanescu, I.; Walters, W. B.

    2010-01-01

    The isomeric and β-decay properties of neutron-rich 53-57 Sc and 53,54 Ca nuclei near neutron number N=32 are reported, and the low-energy level schemes of 53,54,56 Sc and 53-57 Ti are presented. The low-energy level structures of the 21 Sc isotopes are discussed in terms of the coupling of the valence 1f 7/2 proton to states in the corresponding 20 Ca cores. Implications with respect to the robustness of the N=32 subshell closure are discussed, as well as the repercussions for a possible N=34 subshell closure.

  10. Quantum control of isomerization by robust navigation in the energy spectrum

    Energy Technology Data Exchange (ETDEWEB)

    Murgida, G. E., E-mail: murgida@tandar.cnea.gov.ar [Centro Atómico Constituyentes, GIyA, CNEA, San Martín, and Consejo Nacional de Investigaciones Científicas y Técnicas, C1033AAJ Buenos Aires (Argentina); Arranz, F. J., E-mail: fj.arranz@upm.es [Grupo de Sistemas Complejos, Universidad Politécnica de Madrid, 28040 Madrid (Spain); Borondo, F., E-mail: f.borondo@uam.es [Departamento de Química, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid (Spain); Instituto de Ciencias Matemáticas (ICMAT), Cantoblanco, 28049 Madrid (Spain)

    2015-12-07

    In this paper, we present a detailed study on the application of the quantum control technique of navigation in the energy spectrum to chemical isomerization processes, namely, CN–Li⇆ Li–CN. This technique is based on the controlled time variation of a Hamiltonian parameter, an external uniform electric field in our case. The main result of our work establishes that the navigation involved in the method is robust, in the sense that quite sizable deviations from a pre-established control parameter time profile can be introduced and still get good final results. This is specially relevant thinking of a experimental implementation of the method.

  11. Isomeric N-Annulated Perylene Diimide Dimers for Organic Solar Cells.

    Science.gov (United States)

    Ma, Zetong; Fu, Huiting; Meng, Dong; Jiang, Wei; Sun, Yanming; Wang, Zhaohui

    2018-04-16

    Two isomeric N-annulated perylene diimide dimers, namely, p-BDNP and m-BDNP were designed and synthesized via geometric tuning. The distinct molecular geometry and packing arrangements of isomers with almost identical optical and electrochemical properties rendered us an in-depth understanding of the molecular structure-aggregation state-photovoltaic performance relationship. Blended with the commercially available donor PCE-10, p-BDNP and m-BDNP showed distinct differences in photovoltaic performance with power conversion efficiencies (PCEs) of 5.01 % and 4.15 %, respectively. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. g-factor of the 7- isomeric state in 128Ba

    International Nuclear Information System (INIS)

    Kaur, J.; Bansal, N.; Bhati, A.K.; Sharma, V.R.; Kumar, H.; Kumar, R.; Bhowmik, R.K.; Kumar, V.

    2014-01-01

    The time differential perturbed angular distribution technique (TDPAD) has been used to measure the g-factor of the 2396 keV, 7 - isomeric state in 128 Ba. The measured value of g(7 - ) is 1.21 ± 0.01. This value is about 80% higher than the value for the expected configuration of the state and also different in sign. This clearly shows that the configuration of the state does not correspond to the pure two quasineutron configuration that was assigned to it through previous results of in-beam γ-ray spectroscopy

  13. Anesthetic implications of total anomalous systemic venous connection to left atrium with left isomerism

    Directory of Open Access Journals (Sweden)

    Parimala Prasanna Simha

    2012-01-01

    Full Text Available Total anomalous systemic venous connection (TASVC to the left atrium (LA is a rare congenital anomaly. An 11-year-old girl presented with complaints of palpitations and cyanosis. TASVC with left isomerism and noncompaction of LV was diagnosed after contrast echocardiogram and computed tomography angiogram. The knowledge of anatomy and pathophysiology is essential for the successful management of these cases. Anesthetic concerns in this case were polycythemia, paradoxical embolism and rhythm abnormalities. The patient was successfully operated by rerouting the systemic venous connection to the right atrium.

  14. Behavior of the excited deformed band and search for shape isomerism in 184Hg

    International Nuclear Information System (INIS)

    Cole, J.D.; Hamilton, J.H.; Ramayya, A.V.; Nettles, W.G.; Kawakami, H.; Spejewski, E.H.; Ijaz, M.A.; Toth, K.S.; Robinson, E.L.; Sastry, K.S.R.; Lin, J.; Avignone, F.T.; Brantley, W.H.; Rao, P.V.G.

    1976-01-01

    The new isotope 184 Tl has been identified with T 1 / 2 =11 +- 1 sec and the levels in 184 Hg investigated from its decay. The 0 + band head of a deformed band was found to drop to 375 keV in agreement with theoretical predictions. The mean life of the 375-keV 0 + level was measured to be 0.9 +- 0.3 nsec which is a factor of 10 faster than theoretically predicted for a shape-isomeric E2 transition

  15. An infrared study of the nitro—nitrito linkage isomerization in solid nitro- and nitritopentamminecobalt(III) chloride

    Science.gov (United States)

    Heyns, A. M.; de Waal, D.

    1989-01-01

    The photochemical isomerization reaction of [Co(NH 3) 5NO 2]Cl 2 to [Co(NH 3) 5ONO]Cl 2 has been studied in the solid state by means of i.r. spectroscopy. The reaction is first order with k = 2.53±0.05 × 10 -4s -1 and is much faster ( t1/2=49min) than the well-known spontaneous nitrito → nitro isomerization ( t1/2 = 6 days). The i.r. bands of both the NH 3 and ONO - -groups in the range 4000-50 cm -1 indicate minor differences between the structures of freshly and photochemically prepared [Co(NH 3) 5ONO]Cl 2. The far i.r. spectra indicate the disorder existing in the intermediate products during the isomerization processes.

  16. Determination of the isomeric fraction in a postaccelerated radioactive ion beam using the coupled decay-chain equations

    CERN Document Server

    Ekstrom, A; Dijulio, D D; Cederkall, J; Van de Walle, J

    2010-01-01

    A method based on the coupled decay-chain equations for extracting the isotopic and the isomeric composition of a postaccelerated radioactive ion beam is presented and demonstrated on a data set from a Coulomb excitation experiment. This is the first attempt of analyzing the content of a postaccelerated radioactive ion beam using this technique. The beam composition is required for an absolute normalization of the measurement. The strength of the method, as compared to present online-based methods, lies in the determination of the isomeric fraction of a partially isomeric beam using all data accumulated during the experiment. We discuss the limitations and sensitivity of the method with respect to the gamma-ray detection efficiency and the accumulated flux. (C) 2010 Elsevier B.V. All rights reserved.

  17. Photo-isomerization induced rapid photo-degradation of optical nonlinearity in cyano substituted stilbene derivative doped poled polymer

    International Nuclear Information System (INIS)

    Yan Jieyun; Liu Liying; Ji Liyong; Ye Mingxin; Xu Lei; Wang Wencheng

    2004-01-01

    We found that, although alpha'-cyano-4'-nitro-4-N, N-dimethylaminostilbene has larger hyperpolarizability than that of conventional 4'-N, N-dimethylamino-nitrostilbene, the addition of the cyano group makes it much more easy to photo-isomerize, thus destroying the molecular ordering in poled chromophore doped polymers. Experimental evidence was obtained by monitoring the second-harmonic generation intensity, UV-Vis absorption spectrum, and FTIR spectrum. The photo-isomerization reaction process was monitored by optical pump induced absorption anisotropy measurement. Comparisons with the behaviour of a azobenzene dye are also made

  18. Modulating the Physical and Electronic Properties over Positional Isomerism: The Dispirofluorene-Dihydroindacenodithiophene (DSF-IDT) Family.

    Science.gov (United States)

    Peltier, Jean-David; Heinrich, Benoît; Donnio, Bertrand; Jeannin, Olivier; Rault-Berthelot, Joëlle; Poriel, Cyril

    2017-12-06

    We report the first studies on the intrinsic properties of a meta-substituted dihydroindacenodithienyl fragment and more generally the strong impact of positional isomerism on dihydroindacenodithiophene derivatives. The influence of the para and meta linkages has notably been highlighted not only for the electronic properties in solution (electrochemical properties, anodic polymerization, HOMO/LUMO energy levels, optical transitions, fluorescence spectra) but also on the physical properties in the solid state (molecular organization, crystallinity, and phase transitions). The positional isomerism hence appears to be a very efficient tool to drastically tune the properties of dihydroindacenodithiophene derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Isomeric cross-section ratios of some (n,2n) reactions at 14. 7 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Garg, K C; Khurana, C S [Punjabi Univ., Patiala (India). Nuclear Science Labs.

    1979-08-01

    Isomeric cross-section ratios of (n,2n) reactions at 14.7 MeV leading to the millisecond isomeric levels have been calculated theoretically using the statistical theory of nuclear reactions and the spin distribution form due to Bethe and Bloch. The theoretical ratios have been compared with the experimentally measured values in order to evaluate the spin cut-off parameter sigma. This parameter has been used to calculate the effective moment of inertia of the nucleus to draw useful conclusions from the results of present calculations.

  20. First observation of high spin states and isomeric decay in 210Fr

    International Nuclear Information System (INIS)

    Kanjilal, D.; Saha, S.; Bhattacharya, S.; Goswami, A.; Kshetri, R.; Raut, R.; Muralithar, S.; Singh, R. P.; Mukherjee, G.; Mukherjee, B.

    2011-01-01

    The first observation of the prompt and the delayed γ transitions involving the high spin states in 210 Fr is reported. The decay of the high spin states and the isomeric levels of 210 Fr, identified for the first time from the known sequence of low-lying transitions found earlier in the α decay of 214 Ac, were studied. High spin states of the doubly-odd 210 Fr, which were produced by the fusion evaporation reaction 197 Au ( 16 O, xn) 213-x Fr, were populated and the subsequent emitted γ rays were detected through the high-sensitivity germanium clover detector array INGA. The level scheme up to yrast levels of 5.3 MeV excitation energy and ∼20(ℎ/2π) angular momentum could be established for the first time through γγ, γγΔT coincidence, and DCO ratio measurements. A new low-lying isomeric transition at E γ = 203(2) keV was observed. The half-life was measured to be T 1/2 = 41(2) ns. The measured half-life was compared with the corresponding single-particle estimate, based on the level scheme obtained from the experiment.

  1. 1,2-Fluorine Radical Rearrangements: Isomerization Events in Perfluorinated Radicals.

    Science.gov (United States)

    Van Hoomissen, Daniel J; Vyas, Shubham

    2017-11-16

    Devising effective degradation technologies for perfluoroalkyl substances (PFASs) is an active area of research, where the molecular mechanisms involving both oxidative and reductive pathways are still elusive. One commonly neglected pathway in PFAS degradation is fluorine atom migration in perfluoroalkyl radicals, which was largely assumed to be implausible because of the high C-F bond strength. Using density functional theory calculations, it was demonstrated that 1,2-F atom migrations are thermodynamically favored when the fluorine atom migrated from a less branched carbon center to a more branched carbon center. Activation barriers for these rearrangements were within 19-29 kcal/mol, which are possible to easily overcome at elevated temperatures or in photochemically activated species in the gas or aqueous phase. It was also found that the activation barriers for the 1,2-F atom migration are lowered as much as by 10 kcal/mol when common oxidative degradation products such as HF assisted the rearrangements or if the resulting radical center was stabilized by vicinal π-bonds. Natural bond orbital analyses showed that fluorine moves as a radical in a noncharge-separated state. These findings add an important reaction to the existing knowledge of mechanisms for PFAS degradation and highlights the fact that 1,2-F atom shifts may be a small channel for isomerization of these compounds, but upon availability of mineralization products, this isomerization process could become more prominent.

  2. An Insight into Flotation Chemistry of Pyrite with Isomeric Xanthates: A Combined Experimental and Computational Study

    Directory of Open Access Journals (Sweden)

    Guihong Han

    2018-04-01

    Full Text Available The flotation chemistry between pyrite and isomeric xanthates (butyl xanthate and isobutyl xanthate was investigated by means of adsorption experiments, surface tension tests, and molecular dynamic simulations in this work. The flotation chemical results were confirmed and further interpreted by quantum chemical calculations. The experiment results demonstrated that the isobutyl xanthate exhibited superior adsorption capacity and surface activity than those of butyl xanthate in flotation chemistry. In addition, molecular dynamic simulations were simultaneously performed in constant number, constant volume and temperature (NVT, and constant number, constant volume, and pressure (NPT ensemble, indicating that the NPT ensemble was more suitable to the flotation system and the isobutyl xanthate was easier to be adsorbed on pyrite surface compared with butyl xanthate during an appropriate range of concentrations. Furthermore, the quantum chemical calculations elucidated that the isobutyl xanthate presented higher reactivity than that of the corresponding butyl xanthate based on the frontier molecular orbital theory of chemical reactivity, which was consistent with experimental and simulation results obtained. This work can provide theoretical guidance for an in-depth study of the flotation chemistry of pyrite with isomeric xanthates.

  3. In vitro metabolism of nitric oxide-donating aspirin: the effect of positional isomerism.

    Science.gov (United States)

    Gao, Jianjun; Kashfi, Khosrow; Rigas, Basil

    2005-03-01

    NO-donating aspirin (NO-ASA) is a potentially important chemopreventive agent against cancer. Since positional isomerism affects strongly its potency in inhibiting colon cancer cell growth, we studied the metabolic transformations of its ortho-, meta-, and para-isomers in rat liver and colon cytosolic, microsomal, and mitochondrial fractions as well as in intact HT-29 human colon cancer cells. NO-ASA and metabolites were determined by high-performance liquid chromatography and products identified by mass spectroscopy, as required. For all three isomers, the acetyl group on the ASA moiety was hydrolyzed rapidly. This was followed by hydrolysis of the ester bond linking the salicylate anion to the spacer. The ortho- and para-isomers produced salicylic acid and a putative intermediate consisting of the remainder of the molecule, which via a rapid step generated nitrate, (hydroxymethyl)phenol, and a conjugate of spacer with glutathione. The meta-isomer, in contrast, generated salicylic acid and (nitroxymethyl)phenol, the latter leading to (hydroxymethyl)phenol and the glutathione-spacer conjugate. This metabolic pathway takes place in its entirety only in the cytosolic fraction of the tissues tested and in intact human colon cancer cells, perhaps reflecting exposure to the cytosolic glutathione S-transferase, which catalyzes the formation of the spacer-glutathione conjugate. Thus, the three positional isomers of NO-ASA differ in their metabolism and these differences correlate with their differential effects on cancer cell growth, underscoring the importance of positional isomerism in modulating drug effects.

  4. Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

    Science.gov (United States)

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-12-01

    A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S0) electronic state has been constructed by fitting ˜37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm-1. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm-1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.

  5. Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

    International Nuclear Information System (INIS)

    Han, Huixian; Li, Anyang; Guo, Hua

    2014-01-01

    A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S 0 ) electronic state has been constructed by fitting ∼37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm −1 . The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm −1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction

  6. Schiff base switch II precedes the retinal thermal isomerization in the photocycle of bacteriorhodopsin.

    Directory of Open Access Journals (Sweden)

    Ting Wang

    Full Text Available In bacteriorhodopsin, the order of molecular events that control the cytoplasmic or extracellular accessibility of the Schiff bases (SB are not well understood. We use molecular dynamics simulations to study a process involved in the second accessibility switch of SB that occurs after its reprotonation in the N intermediate of the photocycle. We find that once protonated, the SB C15 = NZ bond switches from a cytoplasmic facing (13-cis, 15-anti configuration to an extracellular facing (13-cis, 15-syn configuration on the pico to nanosecond timescale. Significantly, rotation about the retinal's C13 = C14 double bond is not observed. The dynamics of the isomeric state transitions of the protonated SB are strongly influenced by the surrounding charges and dielectric effects of other buried ions, particularly D96 and D212. Our simulations indicate that the thermal isomerization of retinal from 13-cis back to all-trans likely occurs independently from and after the SB C15 = NZ rotation in the N-to-O transition.

  7. Material Balance And Reaction Kinetics Modeling For Penex Isomerization Process In Daura Refinery

    Directory of Open Access Journals (Sweden)

    Hamadi Adel Sharif

    2017-01-01

    Full Text Available Penex Deisohexanizer isomerization of light straight run naphtha is a significant process for petroleum refining and proved to be effective technology to produce gasoline components with a high octane number. Modeling of the chemical kinetic reactions is an important tool because it is a better tool for optimization of the experimental data into parameters used for industrial reactors. The present study deals on the isomerization process in Daura refinery. Material balance calculations were done mathematically on the unit for the kinetics prediction purpose. A kinetic mathematical model was derived for the prediction rate constants K1 and K2 and activation energy Ea at operating temperatures range 120-180°C. According to the model, the results show that with increasing of temperature leads to increased K1 directly, where the K2 values proportional inversely. The activation energy results show that Ea1(nC6

  8. Silver complexation and tandem mass spectrometry for differentiation of isomeric flavonoid diglycosides.

    Science.gov (United States)

    Zhang, Junmei; Brodbelt, Jennifer S

    2005-03-15

    For detection and differentiation of isomeric flavonoids, electrospray ionization mass spectrometry is used to generate silver complexes of the type (Ag + flavonoid)+. Collisionally activated dissociation (CAD) of the resulting 1:1 silver/flavonoid complexes allows isomer differentiation of flavonoids. Eighteen flavonoid diglycosides constituting seven isomeric series are distinguishable from each other based on the CAD patterns of their silver complexes. Characteristic dissociation pathways allow identification of the site of glycosylation, the type of disaccharide (rutinose versus neohesperidose), and the type of aglycon (flavonol versus flavone versus flavanone). This silver complexation method is more universal than previous metal complexation methods, as intense silver complexes are observed even for flavonoids that lack the typical metal chelation sites. To demonstrate the feasibility of using silver complexation and tandem mass spectrometry to characterize flavonoids in complex mixtures, flavonoids extracted from grapefruit juice are separated by high-performance liquid chromatography and analyzed via a postcolumn complexation ESI-MS/MS strategy. Diagnostic fragmentation pathways of the silver complexes of the individual eluting flavonoids allow successful identification of the six flavonoids in the extract.

  9. Isotopic study on mechanism for skeletal isomerization of n-butane over solid acids

    International Nuclear Information System (INIS)

    Suzuki, Tetsuo; Okuhara, Toshio

    2000-01-01

    Reaction mechanism for skeletal isomerization of n-butane over typical strong solid acids were investigated by using 1,4- 13 C 2 -n-butane. We used FI MASS for the analysis of 13 C distribution to get the parent pattern. 13 C-distribution of isobutane formed at 423 K over SO 3 2- /ZrO 2 (SZ) and Cs 2.5 H 0.5 PW 12 O 40 (Cs2.5) were close to binomial distributions, indicating that the isomerization proceeded mainly via a bimolecular mechanism on these catalysts. On the other hand, at 523 K over Cs2.5, the isotopic distribution pattern in isobutane was quite different from the binomial one; the fraction of 13 C 2 -isobutane was much greater than the binomial distribution. This result demonstrates that an intramolecular (monomolecular) rearrangement became significant at 523 K over Cs2.5. The contribution of monomolecular pathway was higher on Cs2.5 than on SZ. We presumed that the contribution of mechanism is related to the acidic property and the dehydrogenation ability of the catalyst. (S.Y.)

  10. Isomeric signatures in the fragmentation of pyridazine and pyrimidine induced by fast ion impact

    Energy Technology Data Exchange (ETDEWEB)

    Wolff, Wania, E-mail: wania@if.ufrj.br; Luna, Hugo; Montenegro, Eduardo C. [Instituto de Física, Universidade Federal do Rio de Janeiro, 21941-972 Rio de Janeiro, RJ (Brazil)

    2015-07-28

    We present fast proton impact induced fragmentations of pyrimidine and pyridazine as an experimental resource to investigate isomeric signatures. Major isomeric imprints are identified for few fragment ions and differences of more than an order of magnitude for the cross sections of fragments of the same mass were measured. The observation of the molecular structure of these isomers gives no apparent indication for the reasons for such substantial differences. It is verified that the simple displacement of the position of one nitrogen atom strongly inhibits or favors the production of some ionic fragment species. The dependency of the fragmentation cross sections on the proton impact energy, investigated by means of time of flight mass spectroscopy and of a model calculation based in first order perturbation theory, allows us to disentangle the complex collision dynamics of the ionic fragments. The proton-induced fragmentation discriminates rather directly the association between a molecular orbital ionization and the fragment-ions creation and abundance, as well as how the redistribution of the energy imparted to the molecules takes place, triggering not only single but also double vacancy and leads to specific fragmentation pathways.

  11. Thermodynamic calculation of simultaneous reactions of n-butane isomerization and isobutane alkylation with ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Batyrshin, N.N.; Beresneva, L.D.; Sidorov, V.A.

    1981-08-01

    Industrial production of ethylene alkylate has gained further development in connection with worldwide ecological problems and the planned changeover of automobile transport to unleaded gasolines, but the scale of production is still substantially less than that of sulfuric acid or hydrogen fluoride alkylates. This is due both to the instability of market prices for ethylene and the shortage of isobutane - a raw material for these large-tonnage production processes and for the synthetic rubber industry. The latter difficulty can be overcome by combining processes of isomerization of n-butane and alkylation of the resultant isobutane with ethylene in a single reaction unit. The possibility of combining these reactions using AlCl/sub 3/-based catalysts has been pointed out previously but in the literature there are no theoretical developments of technology or thermodynamic substantiation of a combined process. We have made a thermodynamic calculation of the consecutive (series-parallel) reactions of isomerization and alkylation with the goal of determining suitable technological conditions for carrying them out simultaneously and establishing the expected equilibrium yields of target products and the compositions of the reaction mixture.

  12. A periodic point-based method for the analysis of Nash equilibria in 2 x 2 symmetric quantum games

    International Nuclear Information System (INIS)

    Schneider, David

    2011-01-01

    We present a novel method of looking at Nash equilibria in 2 x 2 quantum games. Our method is based on a mathematical connection between the problem of identifying Nash equilibria in game theory, and the topological problem of the periodic points in nonlinear maps. To adapt our method to the original protocol designed by Eisert et al (1999 Phys. Rev. Lett. 83 3077-80) to study quantum games, we are forced to extend the space of strategies from the initial proposal. We apply our method to the extended strategy space version of the quantum Prisoner's dilemma and find that a new set of Nash equilibria emerge in a natural way. Nash equilibria in this set are optimal as Eisert's solution of the quantum Prisoner's dilemma and include this solution as a limit case.

  13. A periodic point-based method for the analysis of Nash equilibria in 2 x 2 symmetric quantum games

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, David, E-mail: schneide@tandar.cnea.gov.ar [Departamento de Fisica, Comision Nacional de EnergIa Atomica. Av. del Libertador 8250, 1429 Buenos Aires (Argentina)

    2011-03-04

    We present a novel method of looking at Nash equilibria in 2 x 2 quantum games. Our method is based on a mathematical connection between the problem of identifying Nash equilibria in game theory, and the topological problem of the periodic points in nonlinear maps. To adapt our method to the original protocol designed by Eisert et al (1999 Phys. Rev. Lett. 83 3077-80) to study quantum games, we are forced to extend the space of strategies from the initial proposal. We apply our method to the extended strategy space version of the quantum Prisoner's dilemma and find that a new set of Nash equilibria emerge in a natural way. Nash equilibria in this set are optimal as Eisert's solution of the quantum Prisoner's dilemma and include this solution as a limit case.

  14. Raman spectroscopy, ab-initio model calculations, and conformational, equilibria in ionic liquids

    DEFF Research Database (Denmark)

    Berg, Rolf W.

    2009-01-01

    spectroscopy and ab-initio molecular orbital calculations. A discussion is given, based mainly on some recent FT- Raman spectroscopic results on the model ionic liquid system of 1-butyl-3-methyl-imidazolium ([C4C1Im]+X-) salts. The rotational isomerism of the [C4C1Im]+ cation is described: the presence of anti.......3 Brief introduction to ab-initio model calculations .... 312 12.4 Case study on Raman spectroscopy and structure of imidazolium-based ionic liquids ..... 312 12.5 Raman spectra and structure of [C4C1Im]+ liquids ..... 315 12.6 Normal mode analysis and rotational isomerism of the [C4C1Im]+ cation...

  15. Prediction of high pressure vapor-liquid equilibria with mixing rule using ASOG group contribution method

    Energy Technology Data Exchange (ETDEWEB)

    Tochigi, K.; Kojima, K.; Kurihara, K.

    1985-02-01

    To develop a widely applicable method for predicting high-pressure vapor-liquid equilibria by the equation of state, a mixing rule is proposed in which mixture energy parameter ''..cap alpha..'' of theSoave-RedlichKwong, Peng-Robinson, and Martin cubic equations of state is expressed by using the ASOG group contribution method. The group pair parameters are then determined for 14 group pairs constituted by six groups, i.e. CH/sub 4/, CH/sub 3/, CH/sub 2/, N/sub 2/, H/sub 2/, and CO/sub 2/ groups. By using the group pair parameters determined, high-pressure vapor-liquid equilibria are predicted with good accuracy for binary and ternary systems constituted by n-paraffins, nitrogen, hydrogen, and carbon dioxide in the temperature range of 100 - 450K.

  16. Coexistence of equilibria in a New Keynesian model with heterogeneous beliefs

    International Nuclear Information System (INIS)

    Agliari, Anna; Pecora, Nicolò; Spelta, Alessandro

    2015-01-01

    The recent macroeconomic literature has been stressing the importance of considering heterogeneous expectations while addressing monetary policy. In this paper we consider a standard New Keynesian model, described by a two-dimensional nonlinear map, to analyze the bifurcation structure when agents have heterogeneous expectations and update their beliefs based on past performance. Depending on the degree of reactivity of the monetary policy to inflation and output deviations from the target equilibrium, different kind of dynamics may occur. We find that multiple equilibria and complicated dynamics, associated to codimension-2 bifurcations, may arise even if the monetary policy is set to respond more than point for point to inflation, as the Taylor principle prescribes. We show that if the monetary policy accommodates for a sufficient degree of output stabilization, complicated dynamics can be avoided and the number of coexisting equilibria reduces.

  17. Experimental investigation of phase equilibria in the Zr-Cu-Ni ternary system

    International Nuclear Information System (INIS)

    Yang, Mujin; Wang, Cuiping; Yang, Shuiyuan; Shi, Zhan; Han, Jiajia; Liu, Xingjun

    2017-01-01

    The phase equilibria in the Zr-Cu-Ni ternary system are investigated combined with X-ray diffraction, electron probe micro-analysis and differential scanning calorimetry. Two isothermal sections of the Zr-Cu-Ni ternary system at 1 000 C and 1 100 C are experimentally established. Most of the binary intermetallic compounds, e.g. Zr 7 Ni 10 , ZrNi, ZrNi 5 , Zr 14 Cu 51 , and Zr 2 Cu 9 , show a remarkable ternary solubility. A new ternary compound named τ 3 (Zr 31.1-30.7 . Cu 28.5-40.3 Ni 40.4-29.0 ) is detected at 1 000 C and dissolved at 1 020 C because the nearby large liquid phase field further expands. The newly determined phase equilibria will provide important information for both thermodynamic assessment and alloy design of Zr-based metallic glass.

  18. Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

    Science.gov (United States)

    Circone, S.; Kirby, S.H.; Stern, L.A.

    2006-01-01

    Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

  19. Experimental investigation of phase equilibria in the Ni-Nb-V ternary system

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xingjun; Yang, Shuiyuan; Wang, Cuiping [Xiamen Univ. (China). Dept. of Materials Science and Engineering; Xiamen Univ. (China). Fujian Provincial Key Lab. of Materials Genome; Zhang, Xianjie; Jiang, Hengxing; Shi, Zhan [Xiamen Univ. (China). Dept. of Materials Science and Engineering

    2017-09-15

    The phase equilibria of the Ni-Nb-V ternary system at 1000 C and 1200 C were established using electron probe microanalysis, X-ray diffraction and differential scanning calorimetry. The results of the investigation revealed that: (1) The Nb solubility in (Ni) and σ{sup '} phases was less than 10 at.%; (2) A ternary compound τ (NiNbV) was confirmed, in which V had a large solubility; (3) A new liquid region was evident at 1200 C, but was absent at 1000 C; (4) The lattice constants of Ni{sub 3}Nb and Ni{sub 6}Nb{sub 7} phase decreased with increase in V content in the Ni{sub 3}Nb and Ni{sub 6}Nb{sub 7}. The phase equilibria of the Ni-Nb-V ternary system will contribute to its thermodynamic assessment.

  20. Edge stability and pedestal profile sensitivity of snowflake diverted equilibria in the TCV Tokamak

    International Nuclear Information System (INIS)

    Medvedev, S.Yu.; Ivanov, A.A.; Martynov, A.A.; Poshekhonov, Yu.Yu.; Behn, R.; Martin, Y.R.; Moret, J.M.; Piras, F.; Pitzschke, A.; Pochelon, A.; Sauter, O.; Villard, L.

    2010-01-01

    A second order null divertor (snowflake) has been successfully created and controlled in the TCV tokamak[1] (F. Piras et al., Plasma Phys. Control. Fusion, 2009). The results of ideal MHD edge stability computations show an enhancement of the edge stability properties of the snowflake equilibria compared to standard x-point configurations[2] (S. Yu. Medvedev et al., 36th EPS Conference on Plasma Physics, 2009). However, a sensitivity study of the stability limits to variations of the pedestal profiles is essential for making conclusions about possibilities of ELM control in snowflake plasmas. Variations of the edge stability and beta limits for several types of snowflake equilibria, different values of triangularity and various pedestal profiles are investigated (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  1. High-pressure phase equilibria in the (carbon dioxide + 1-hexanol) system

    International Nuclear Information System (INIS)

    Secuianu, Catinca; Feroiu, Viorel; Geana, Dan

    2010-01-01

    (Vapour + liquid) equilibria (VLE) and (vapour + liquid + liquid) equilibria (VLLE) data for the (carbon dioxide + 1-hexanol) system were measured at (293.15, 303.15, 313.15, 333.15, and 353.15) K. Phase behaviour measurements were made in a high-pressure visual cell with variable volume, based on the static-analytic method. The pressure range under investigation was between (0.6 and 14.49) MPa. The Soave-Redlich-Kwong (SRK) equation of state (EOS) with classical van der Waals mixing rules (two-parameters conventional mixing rule, 2PCMR), was used in a semi-predictive approach, in order to represent the complex phase behaviour (critical curve, LLV line, isothermal VLE, LLE, and VLLE) of the system. The topology of phase behaviour is reasonably well predicted.

  2. Strategic trade between two regions with partial local consumer protection - General setup and nash equilibria

    Science.gov (United States)

    Iordanov, Iordan V.; Vassilev, Andrey A.

    2017-12-01

    We construct a model of the trade relations between two regions for the case when the trading entities (consumers) compete for a scarce good and there is an element of strategic interdependence in the trading process. Additionally, local consumers enjoy partial protection in the form of guaranteed access to a part of the locally-supplied quantity of the good. The model is formulated for the general asymmetric case, where the two regions differ in terms of parameters such as income, size of the local market supply, degree of protection and transportation costs. For this general model we establish the existence of Nash equilibria and obtain their form as a function of the model parameters, producing a typology of the equilibria. This is a required step in order to rigorously study various types of price dynamics for the model.

  3. Experimental investigation of undesired stable equilibria in pumpkin shape super-pressure balloon designs

    Science.gov (United States)

    Schur, W. W.

    2004-01-01

    Excess in skin material of a pneumatic envelope beyond what is required for minimum enclosure of a gas bubble is a necessary but by no means sufficient condition for the existence of multiple equilibrium configurations for that pneumatic envelope. The very design of structurally efficient super-pressure balloons of the pumpkin shape type requires such excess. Undesired stable equilibria in pumpkin shape balloons have been observed on experimental pumpkin shape balloons. These configurations contain regions with stress levels far higher than those predicted for the cyclically symmetric design configuration under maximum pressurization. Successful designs of pumpkin shape super-pressure balloons do not allow such undesired stable equilibria under full pressurization. This work documents efforts made so far and describes efforts still underway by the National Aeronautics and Space Administration's Balloon Program Office to arrive on guidance on the design of pumpkin shape super-pressure balloons that guarantee full and proper deployment.

  4. Measurement and modeling of high-pressure (vapour + liquid) equilibria of (CO2 + alcohol) binary systems

    International Nuclear Information System (INIS)

    Gutierrez, Jorge E.; Bejarano, Arturo; Fuente, Juan C. de la

    2010-01-01

    An apparatus based on a static-analytic method assembled in this work was utilized to perform high pressure (vapour + liquid) equilibria measurements with uncertainties estimated at 2 + 1-propanol), (CO 2 + 2-methyl-1-propanol), (CO 2 + 3-methyl-1-butanol), and (CO 2 + 1-pentanol) binary systems at temperatures of (313, 323, and 333) K, and at pressure range of (2 to 12) MPa. For all the (CO 2 + alcohol) systems, it was visually monitored to insure that there was no liquid immiscibility at the temperatures and pressures studied. The experimental results were correlated with the Peng-Robinson equation of state using the quadratic mixing rules of van der Waals with two adjustable parameters. The calculated (vapour + liquid) equilibria compositions were found to be in good agreement with the experimental values with deviations for the mol fractions <0.12 and <0.05 for the liquid and vapour phase, respectively.

  5. Stability of highly shifted equilibria in a large aspect ratio low-field tokamak

    International Nuclear Information System (INIS)

    Gourdain, P.-A.; Leboeuf, J.-N.; Neches, R. Y.

    2007-01-01

    In the long run, the economics of fusion will dictate that reactors confine large plasma pressure rather efficiently. A possible route manifests itself as equilibria with large shift of the plasma magnetic axis. This shift compresses the flux surfaces on the outer part of the plasma, hereby increasing the allowable plasma pressure a machine can confine for a given toroidal magnetic field, which is the main cost of the device. As a first step toward a reactor, we propose investigating the stability of such configurations in a low magnetic field high aspect ratio machine. By focusing our arguments solely on the shape of the toroidal plasma current density profile we discuss the stability of highly shifted equilibria and their robustness to current profile variations that could occur in actual experiments. The evolution of the plasma parameters, as the beta poloidal is increased, is also examined to give a better understanding of the difference in performance between the various regimes

  6. Graphical Derivatives and Stability Analysis for Parameterized Equilibria with Conic Constraints

    Czech Academy of Sciences Publication Activity Database

    Mordukhovich, B. S.; Outrata, Jiří; Ramírez, H. C.

    2015-01-01

    Roč. 23, č. 4 (2015), s. 687-704 ISSN 1877-0533 R&D Projects: GA ČR(CZ) GAP201/12/0671 Institutional support: RVO:67985556 Keywords : Variational analysis and optimization * Parameterized equilibria * Conic constraints * Sensitivity and stability analysis * Solution maps * Graphical derivatives * Normal and tangent cones Subject RIV: BA - General Mathematics Impact factor: 0.973, year: 2015 http://library.utia.cas.cz/separaty/2015/MTR/outrata-0449259.pdf

  7. Bifurcation of equilibria between with and without a large island in the large helical device

    Energy Technology Data Exchange (ETDEWEB)

    Ohyabu, N; Narushima, Y; Nagayama, Y; Narihara, K; Morisaki, T; Komori, A [National Institute for Fusion Science, Toki, Gifu, 509-5292 (Japan)

    2005-09-01

    A rapid bifurcation of the equilibria with and without a large island (n/m = 1/1) has been observed in the medium to high beta large helical device discharges. A large island imposed by an external resonant field is suddenly suppressed nearly perfectly by the plasma effects when the beta at the {iota}/2{pi} = 1 surface exceeds a critical value. The critical beta value is nearly proportional to the externally imposed resonant field normalized by the main field strength.

  8. Exact solutions for helical magnetohydrodynamic equilibria. II. Nonstatic and nonbarotropic solutions

    International Nuclear Information System (INIS)

    Villata, M.; Ferrari, A.

    1994-01-01

    In the framework of the analytical study of magnetohydrodynamic (MHD) equilibria with flow and nonuniform density, a general family of well-behaved exact solutions of the generalized Grad--Shafranov equation and of the whole set of time-independent MHD equations completed by the nonbarotropic ideal gas equation of state is obtained, both in helical and axial symmetry. The helical equilibrium solutions are suggested to be relevant to describe the helical morphology of some astrophysical jets

  9. Belief-Based Equilibria in the Repeated Prisoners' Dilemma with Private Monitoring

    OpenAIRE

    V. Bhaskar; Ichiro Obara

    2000-01-01

    We analyze the infinitely repeated prisoners' dilemma with imperfect private monitoring and discounting. The main contribution of this paper is to construct ``belief-based'' strategies, where a player's continuation strategy is a function only of his beliefs. This simplifies the analysis considerably, and allows us to explicitly construct sequential equilibria for such games, thus enabling us to invoke the one-step deviation principle of dynamic programming. By doing so, we prove that one can...

  10. The computation of multiple MHD equilibria in axisymmetric and straight geometry

    International Nuclear Information System (INIS)

    Thomas, C.Ll.

    1979-01-01

    The details of the numerical methods used in codes for computing MHD equilibria in discrete conductor configurations are described with both code users and code writers in mind. Results produced by the codes have been successfully verified against analytic results and independent computations. The axisymmetric code has proved to be a valuable diagnostic aid for the TOSCA experiment. The user images of the codes are described in the appendices. (author)

  11. Equilibria in aqueous cadmium-chloroacetate-glycinate systems. A convolution-deconvolution cyclic voltammetric study

    International Nuclear Information System (INIS)

    Abdel-Hamid, R.; Rabia, M.K.M.

    1994-01-01

    Stability constants and composition of cadmium-glycinate binary complexes were determined using cyclic voltammetry. Furthermore, binary and ternary complex equilibria for chloroacetates and glycinate with cadmium in 0.1 M aqueous KNO 3 at pH 10.4 and 298 K were investigated. Cadmium forms binary complexes with chloroacetates of low stability and ternary ones with chloroacetate-glycinate of significant stability. (author)

  12. Learned helplessness, discouraged workers, and multiple unemployment equilibria in a search model

    OpenAIRE

    Bjørnstad, Roger

    2001-01-01

    Abstract: Unemployment varies strongly between countries with comparable economic structure. Some economists have tried to explain these differences with institutional differences in the labour market. Instead, this paper focuses on a model with multiple equilibria so that the same socioeconomic structure can give rise to different levels of unemployment. Unemployed workers' search efficiency are modelled within an equilibrium search model and lay behind these results. In the model learned...

  13. Chemical exchange equilibria in isotope separation. Part I : Evaluation of separation factors

    International Nuclear Information System (INIS)

    Dave, S.M.

    1980-01-01

    The theory of chemical exchange equilibria as applied to the isotope separation processes and the isotope effects on equilibrium constants of different exchange reactions has come a long way since its inception by Urey and Rittenberg. An attempt has been made to bring relevant information together and present a unified approach to isotopic chemical exchange equilibrium constant evaluation and its implications to separation processes. (auth.)

  14. The empirical content of models with multiple equilibria in economies with social interactions

    OpenAIRE

    Alberto Bisin; Andrea Moro; Giorgio Topa

    2011-01-01

    We study a general class of models with social interactions that might display multiple equilibria. We propose an estimation procedure for these models and evaluate its efficiency and computational feasibility relative to different approaches taken to the curse of dimensionality implied by the multiplicity. Using data on smoking among teenagers, we implement the proposed estimation procedure to understand how group interactions affect health-related choices. We find that interaction effects a...

  15. Three-dimensional tokamak equilibria in the presence of resonant field errors

    International Nuclear Information System (INIS)

    Reiman, A.; Monticello, D.

    1992-01-01

    Numerical solutions are described for three-dimensional MHD equilibria in the presence of resonant magnetic field perturbations. The effects of a realistic spectrum of resonant field errors are calculated for a range of current profiles. It is found that field errors of the magnitude existing in present day devices, and contemplated for future devices, can produce a set of magnetic islands occupying a significant fraction of the plasma cross-section

  16. Alpha spectrometry of thick sources. II. Application to the study of radioactive equilibria in uranium ores

    International Nuclear Information System (INIS)

    Acena Barrenechea, M.L.; Tormo Ferrero, M.J.

    1977-01-01

    A method for determining nuclide activities in 4n + 2 uranium series using alpha spectrometry of thick sources is described. This method has been applied to several uranium ores, showing different states of radioactive equilibria. The spectra from samples prepared by cold compression show some anomalies, due to the evolution and later decay of 219 Rn and daughters. This phenomenon must be taken in consideration when computing spectra line intensities. (author) [es

  17. A thermodynamic solution model for calcium carbonate: Towards an understanding of multi-equilibria precipitation pathways

    OpenAIRE

    Donnet, Marcel; Bowen, Paul; Lemaître, Jacques

    2009-01-01

    Thermodynamic solubility calculations are normally only related to thermodynamic equilibria in solution. In this paper, we extend the use of such solubility calculations to help elucidate possible precipitation reaction pathways during the entire reaction. We also estimate the interfacial energy of particles using only solubility data by a modification of Mersmann’s approach. We have carried this out by considering precipitation reactions as a succession of small quasi-equilibrium states. Thu...

  18. Solid-Liquid Equilibria in Systems [Cxmim][Tf2N] with Diethylamine

    Czech Academy of Sciences Publication Activity Database

    Rotrekl, Jan; Vrbka, P.; Sedláková, Zuzana; Wagner, Zdeněk; Jacquemin, J.; Bendová, Magdalena

    2015-01-01

    Roč. 87, č. 5 (2015), s. 453-460 ISSN 0033-4545. [International Symposium on Solubility Phenomena 2014. Karlsruhe, 20.07.2014-24.07.2014] R&D Projects: GA MŠk(CZ) LD14094; GA MŠk LG13060 Institutional support: RVO:67985858 Keywords : ionic liquids * solid-liquid equilibria * COSMO-RS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.615, year: 2015

  19. Isomeric and high-spin states of 94Tc and the search for yrast isomers near Napprox.50

    International Nuclear Information System (INIS)

    Lee, I.Y.; Johnson, N.R.; McGowan, F.K.; Young, G.R.; Guidry, M.W.; Yates, S.W.

    1981-01-01

    A search for isomers in the Napprox.50 region has produced no evidence of high-spin yrast isomerism. A new 4.5-ns low-multiplicity isomer has been identified and assigned to 94 Tc, while the yrast sequence of 94 Tc has been established to more than 5 MeV in excitation energy

  20. Synthesis of Heterocycles through a Ruthenium‐Catalyzed Tandem Ring‐Closing Metathesis/Isomerization/N‐Acyliminium Cyclization Sequence

    DEFF Research Database (Denmark)

    Ascic, Erhad; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

    2011-01-01

    Tandem bicycle: In the title reaction double bonds created during ring-closing metathesis isomerize to generate reactive iminium intermediates that undergo intramolecular cyclization reactions with tethered heteroatom and carbon nucleophiles. In this way, a series of biologically interesting hete...... heterocyclic compounds can be made, including a known precursor for the total synthesis of the antiparasitic natural product harmicine....

  1. Ruthenium Stilbenyl and Diruthenium Distyrylethene Complexes: Aspects of Electron Delocalization and Electrocatalyzed Isomerization of the Z-Isomer

    Czech Academy of Sciences Publication Activity Database

    Linseis, M.; Záliš, Stanislav; Zabel, M.; Winter, R. F.

    2012-01-01

    Roč. 134, č. 40 (2012), s. 16671-16692 ISSN 0002-7863 R&D Projects: GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : CIS-TRANS-ISOMERIZATION * MIXED-VALENCE COMPOUNDS * VIBRATIONAL TIME -SCALE Subject RIV: CG - Electrochemistry Impact factor: 10.677, year: 2012

  2. Valence isomerization of 2-phospha-4-silabicyclo[1.1.0]butane: a high-level ab initio study

    NARCIS (Netherlands)

    Slootweg, J.C.; Ehlers, A.W.; Lammertsma, K.

    2006-01-01

    The rearrangements for 2-phospha-4-silabicyclo[1.1.0]butane, analogous to the valence isomerization of the hydrocarbons bicyclobutane, 1,3-butadiene, and cyclobutene, were studied at the (U)QCISD(T)/ 6-311+G**//(U)QCISD/6-31G* level of theory. The monocyclic 1,2-dihydro-1,2-phosphasiletes are shown

  3. Measurements of 14-MeV neutron cross-sections for the production of isomeric states in hafnium isotopes

    International Nuclear Information System (INIS)

    Patrick, B.H.; Sowerby, M.G.; Wilkins, C.G.; Russen, L.C.

    1990-01-01

    The cross sections for the production of isomeric states in the reactions 179 Hf(n,2n) 178m2 Hf, 180 Hf(n,2n) 179m2 Hf, 179 Hf(n,n') 179m2 Hf with 14 MeV neutrons have been measured and compared with the theoretical ones. 4 refs, 3 figs, 4 tabs

  4. Anion-assisted trans-cis isomerization of palladium(II) phosphine complexes containing acetanilide functionalities through hydrogen bonding interactions.

    Science.gov (United States)

    Lu, Xiao-Xia; Tang, Hau-San; Ko, Chi-Chiu; Wong, Jenny Ka-Yan; Zhu, Nianyong; Yam, Vivian Wing-Wah

    2005-03-28

    The anion-assisted shift of trans-cis isomerization equilibrium of a palladium(II) complex containing acetanilide functionalities brought about by allosteric hydrogen bonding interactions has been established by UV/Vis, 1H NMR, 31P NMR and ESI-MS studies.

  5. Investigation of the interaction between isomeric derivatives and human serum albumin by fluorescence spectroscopy and molecular modeling

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ruiyong, E-mail: wangry@zzu.edu.cn; Dou, Huanjing; Yin, Yujing; Xie, Yuanzhe; Sun, Li; Liu, Chunmei; Dong, Jingjing; Huang, Gang; Zhu, Yanyan; Song, Chuanjun, E-mail: chjsong@zzu.edu.cn; Chang, Junbiao, E-mail: changjunbiao@zzu.edu.cn

    2014-10-15

    In this paper, we have synthesized 9H-pyrrolo[1,2-a]indol-9-ones and the isomeric indeno[2,1-b]pyrrol-8-ones. The interactions of human serum albumin with series of isomeric derivatives have been studied by spectrophotometric methods. Results show the intrinsic fluorescence is quenched by the derivatives with a static quenching procedure. The thermodynamics parameters indicate that van der Waals forces and hydrogen bonds play a major role in the interactions. The results of synchronous fluorescence spectra demonstrate that the microenvironments of Trp residue of human serum albumin are disturbed by most derivatives. Thermodynamic results showed that the 9H-pyrrolo[1,2-a]indol-9-ones are stronger quenchers and bind to human serum albumin with the higher affinity than isomeric indeno[2,1-b]pyrrol-8-ones. The influence of molecular structure on the binding aspects has been investigated. - Highlights: • The interactions between isomeric derivatives and HSA have been investigated. • Results reveal that 9H-pyrrolo[1,2-a]indol-9-ones are stronger quenchers for HSA. • Hydrogen bonds and van der Waals forces play major role in the binding process. • The influence of molecular structure on the binding aspects has been investigated. • The binding study was also modeled by molecular docking.

  6. Investigation of the interaction between isomeric derivatives and human serum albumin by fluorescence spectroscopy and molecular modeling

    International Nuclear Information System (INIS)

    Wang, Ruiyong; Dou, Huanjing; Yin, Yujing; Xie, Yuanzhe; Sun, Li; Liu, Chunmei; Dong, Jingjing; Huang, Gang; Zhu, Yanyan; Song, Chuanjun; Chang, Junbiao

    2014-01-01

    In this paper, we have synthesized 9H-pyrrolo[1,2-a]indol-9-ones and the isomeric indeno[2,1-b]pyrrol-8-ones. The interactions of human serum albumin with series of isomeric derivatives have been studied by spectrophotometric methods. Results show the intrinsic fluorescence is quenched by the derivatives with a static quenching procedure. The thermodynamics parameters indicate that van der Waals forces and hydrogen bonds play a major role in the interactions. The results of synchronous fluorescence spectra demonstrate that the microenvironments of Trp residue of human serum albumin are disturbed by most derivatives. Thermodynamic results showed that the 9H-pyrrolo[1,2-a]indol-9-ones are stronger quenchers and bind to human serum albumin with the higher affinity than isomeric indeno[2,1-b]pyrrol-8-ones. The influence of molecular structure on the binding aspects has been investigated. - Highlights: • The interactions between isomeric derivatives and HSA have been investigated. • Results reveal that 9H-pyrrolo[1,2-a]indol-9-ones are stronger quenchers for HSA. • Hydrogen bonds and van der Waals forces play major role in the binding process. • The influence of molecular structure on the binding aspects has been investigated. • The binding study was also modeled by molecular docking

  7. Prediction of vapour-liquid equilibria for the kinetic study of processes based on synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Di Serio, M.; Tesser, R.; Cozzolino, M.; Santacesaria, E. [Naples Univ., Napoli (Italy). Dept. of Chemistry

    2006-07-01

    Syngas is normally used in the production of a broad range of chemicals and fuels. In many of these processes multiphase reactors, gas-liquid or gas-liquid-solid are used. Kinetic studies in multiphase systems are often complicated by the non-ideal behaviour of reagents and/or products that are consistently partitioned between the liquid and the vapour phase. Moreover, as often kinetic data are collected in batch conditions for the liquid phase, activity coefficients of the partitioned components can consistently change during the time as a consequence of changing the composition of the reaction mixture. Therefore, it is necessary, in these cases, to known the vapor-liquid equilibria (VLE) in order to collect and to interpret correctly the kinetic data. The description of phase equilibria, at high pressures, is usually performed by means of an EOS (Equation of State) allowing the calculation of fugacity coefficients, for each component, in both phases and determining the partition coefficients but the EOS approach involves the experimental determination of the interaction parameters for all the possible binary system of the mixture. For multicomponent mixtures a complete experimental determination of vapourliquid equilibria is very hard, also considering the high pressure and temperatures used. Some predictive group contribution methods have been recently developed. In this paper, we will describe in detail the application of these methods to the methanol homologation, as an example, with the scope of determining more reliable kinetic parameters for this reaction. (orig.)

  8. Ternary (liquid + liquid) equilibria of {bis(trifluoromethylsulfonyl)-amide based ionic liquids + butan-1-ol + water}

    International Nuclear Information System (INIS)

    Marciniak, Andrzej; Wlazło, Michał; Gawkowska, Joanna

    2016-01-01

    Highlights: • Ternary (liquid + liquid) equilibria for 3 ionic liquid + butanol + water systems. • The influence of ionic liquid structure on phase diagrams is discussed. • Influence of IL structure on S and β for butanol/water separation is discussed. - Abstract: Ternary (liquid + liquid) phase equilibria for 3 systems containing bis(trifluoromethylsulfonyl)-amide ionic liquids (1-buthyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide, 1-(2-methoxyethyl)-1-methylpiperidinium bis(trifluoromethylsulfonyl)-amide, {1-(2-methoxyethyl)-1-methylpyrrolidinium bis(trifluorylsulfonyl)-amide) + butan-1-ol + water} have been determined at T = 298.15 K. The selectivity and solute distribution ratio were calculated for investigated systems and compared with literature data for other systems containing ionic liquids. In each system total solubility of butan-1-ol and low solubility of water in the ionic liquid is observed. The experimental results have been correlated using NRTL model. The influence of the structure of ionic liquid on phase equilibria, selectivity and solute distribution ratio is shortly discussed.

  9. Measurement and modeling of high-pressure (vapor + liquid) equilibria of (CO2 + alkanol) binary systems

    International Nuclear Information System (INIS)

    Bejarano, Arturo; Gutierrez, Jorge E.; Araus, Karina A.; Fuente, Juan C. de la

    2011-01-01

    Research highlights: → (Vapor + liquid) equilibria of three (CO 2 + C 5 alcohol) binary systems were measured. → Complementary data are reported at (313, 323 and 333) K and from (2 to 11) MPa. → No liquid immiscibility was observed at the temperatures and pressures studied. → Experimental data were correlated with the PR-EoS and the van de Waals mixing rules. → Correlation results showed relative deviations ≤8 % (liquid) and ≤2 % (vapor). - Abstract: Complementary isothermal (vapor + liquid) equilibria data are reported for the (CO 2 + 3-methyl-2-butanol), (CO 2 + 2-pentanol), and (CO 2 + 3-pentanol) binary systems at temperatures of (313, 323, and 333) K, and at pressure range of (2 to 11) MPa. For all (CO 2 + alcohol) systems, it was visually monitored that there was no liquid immiscibility at the temperatures and pressures studied. The experimental data were correlated with the Peng-Robinson equation of state using the quadratic mixing rules of van der Waals with two adjustable parameters. The calculated (vapor + liquid) equilibria compositions were found to be in good agreement with the experimental data with deviations for the mole fractions <8% and <2% for the liquid and vapor phase, respectively.

  10. Description of gas hydrates equilibria in sediments using experimental data of soil water potential

    Energy Technology Data Exchange (ETDEWEB)

    Istomin, V. [NOVATEK, Moscow (Russian Federation); Chuvilin, E. [Moscow State Univ., Moscow (Russian Federation). Dept. of Geology; Makhonina, N.; Kvon, V. [VNIIGAZ, Moscow (Russian Federation); Safonov, S. [Schlumberger Moscow Research, Moscow (Russian Federation)

    2008-07-01

    Analytical relationships have been developed between hydrate dissociation pressure and vapor pressure above the pore water surface. In addition, experiments have been discussed in numerous publications on the effect of narrow interconnected throats between pores on clathrate dissociation conditions in porous media. This paper presented an approach that improved upon the available thermodynamic methods for calculation of hydrate phase equilibria. The approach took into account the properties of pore water in natural sediments including three-phase equilibrium of gas-pore water-gas hydrate in a similar way as for unfrozen water in geocryology science. The purpose of the paper was to apply and adapt geocryology and soil physics method to the thermodynamic calculation of non-clathrated water content in sediments. It answered the question of how to estimate the non-clathrated water content if pore water potential was known. The paper explained the thermodynamics of water phase in porous media including the thermodynamic properties of supercooled water, the thermodynamic properties of pore water and pore ice in sediments, and the phase equilibria of pore water. The paper also discussed the quantitative techniques that were utilized for determination of unfrozen water content in sediments and its dependence on temperature variation. These included contact-saturation, calorimetric, dielectric, nuclear magnetic resonance, and others. The thermodynamic calculations of pore water phase equilibria were also presented. 30 refs., 5 tabs., 8 figs.

  11. Density-functional study on the equilibria in the ThDP activation.

    Science.gov (United States)

    Delgado, Eduardo J; Alderete, Joel B; Jaña, Gonzalo A

    2011-11-01

    The equilibria among the various ionization and tautomeric states involved in the activation of ThDP is addressed using high level density functional theory calculations, X3LYP/6-311++G(d,p)//X3LYP(PB)/6-31++G(d,p). This study provides the first theoretically derived thermodynamic data for the internal equilibria in the activation of ThDP. The role of the medium polarity on the geometry and thermodynamics of the diverse equilibria of ThDP is addressed. The media chosen are cyclohexane and water, as paradigms of apolar and polar media. The results suggest that all ionization and tautomeric states are accessible during the catalytic cycle, even in the absence of substrate, being APH(+) the form required to interconvert the AP and IP tautomers; and the generation of the ylide proceeds via the formation of the IP form. Additionally, the calculated ΔG° values allow to calculate all the equilibrium constants, including the pK(C2) for the thiazolium C2 atom whose ionization is believed to initiate the catalytic cycle.

  12. (Liquid + liquid) equilibria for (water + 1-propanol or acetone + β-citronellol) at different temperatures

    International Nuclear Information System (INIS)

    Li, Hengde; Han, Yongtao; Huang, Cheng; Yang, Chufen

    2015-01-01

    Graphical abstract: (Liquid + liquid) equilibrium data for systems composed of β-citronellol and aqueous 1-propanol or acetone are presented. Distribution ratios of 1-propanol and acetone in the mixtures are examined. The effect of the temperature on the ternary (liquid + liquid) equilibria is evaluated and discussed. - Highlights: • Ternary (liquid + liquid) equilibria containing β-citronellol are presented. • Distribution ratios of 1-propanol and acetone in the mixtures are examined. • The effect on the temperature of the systems is evaluated and discussed. - Abstract: On this paper, experimental (liquid + liquid) equilibrium (LLE) results are presented for systems composed of β-citronellol and aqueous 1-propanol or acetone. To evaluate the phase separation properties of β-citronellol in aqueous mixtures, LLE values for the ternary systems (water + 1-propanol + β-citronellol) and (water + acetone + β-citronellol) were determined with a tie-line method at T = (283.15, 298.15, and 313.15 ± 0.02) K and atmospheric pressure. The reliability of the experimental tie-lines was verified by the Hand and Bachman equations. Ternary phase diagrams, distribution ratios of 1-propanol and acetone in the mixtures are shown. The effect of the temperature on the ternary (liquid + liquid) equilibria was examined and discussed. The experimental LLE values were satisfactorily correlated by extended UNIQUAC and modified UNIQUAC models

  13. Effect of temperature on acid-base equilibria in separation techniques. A review.

    Science.gov (United States)

    Gagliardi, Leonardo G; Tascon, Marcos; Castells, Cecilia B

    2015-08-19

    Studies on the theoretical principles of acid-base equilibria are reviewed and the influence of temperature on secondary chemical equilibria within the context of separation techniques, in water and also in aqueous-organic solvent mixtures, is discussed. In order to define the relationships between the retention in liquid chromatography or the migration velocity in capillary electrophoresis and temperature, the main properties of acid-base equilibria have to be taken into account for both, the analytes and the conjugate pairs chosen to control the solution pH. The focus of this review is based on liquid-liquid extraction (LLE), liquid chromatography (LC) and capillary electrophoresis (CE), with emphasis on the use of temperature as a useful variable to modify selectivity on a predictable basis. Simplified models were evaluated to achieve practical optimizations involving pH and temperature (in LLE and CE) as well as solvent composition in reversed-phase LC. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Theoretical models of non-Maxwellian equilibria for one-dimensional collisionless plasmas

    Science.gov (United States)

    Allanson, O.; Neukirch, T.; Wilson, F.; Troscheit, S.

    2016-12-01

    It is ideal to use exact equilibrium solutions of the steady state Vlasov-Maxwell system to intialise collsionless simulations. However, exact equilibrium distribution functions (DFs) for a given macroscopic configuration are typically unknown, and it is common to resort to using `flow-shifted' Maxwellian DFs in their stead. These DFs may be consistent with a macrosopic system with the target number density and current density, but could well have inaccurate higher order moments. We present recent theoretical work on the `inverse problem in Vlasov-Maxwell equilibria', namely calculating an exact solution of the Vlasov equation for a specific given magnetic field. In particular, we focus on one-dimensional geometries in Cartesian (current sheets) coordinates.1. From 1D fields to Vlasov equilibria: Theory and application of Hermite Polynomials: (O. Allanson, T. Neukirch, S. Troscheit and F. Wilson, Journal of Plasma Physics, 82, 905820306 (2016) [28 pages, Open Access] )2. An exact collisionless equilibrium for the Force-Free Harris Sheet with low plasma beta: (O. Allanson, T. Neukirch, F. Wilson and S. Troscheit, Physics of Plasmas, 22, 102116 (2015) [11 pages, Open Access])3. Neutral and non-neutral collisionless plasma equilibria for twisted flux tubes: The Gold-Hoyle model in a background field (O. Allanson, F. Wilson and T. Neukirch, (2016)) (accepted, Physics of Plasmas)

  15. Nitrite-reductase and peroxynitrite isomerization activities of Methanosarcina acetivorans protoglobin.

    Directory of Open Access Journals (Sweden)

    Paolo Ascenzi

    Full Text Available Within the globin superfamily, protoglobins (Pgb belong phylogenetically to the same cluster of two-domain globin-coupled sensors and single-domain sensor globins. Multiple functional roles have been postulated for Methanosarcina acetivorans Pgb (Ma-Pgb, since the detoxification of reactive nitrogen and oxygen species might co-exist with enzymatic activity(ies to facilitate the conversion of CO to methane. Here, the nitrite-reductase and peroxynitrite isomerization activities of the CysE20Ser mutant of Ma-Pgb (Ma-Pgb* are reported and analyzed in parallel with those of related heme-proteins. Kinetics of nitrite-reductase activity of ferrous Ma-Pgb* (Ma-Pgb*-Fe(II is biphasic and values of the second-order rate constant for the reduction of NO2- to NO and the concomitant formation of nitrosylated Ma-Pgb*-Fe(II (Ma-Pgb*-Fe(II-NO are k(app1= 9.6 ± 0.2 M(-1 s(-1 and k(app2 = 1.2 ± 0.1 M(-1 s(-1 (at pH 7.4 and 20 °C. The k(app1 and k(app2 values increase by about one order of magnitude for each pH unit decrease, between pH 8.3 and 6.2, indicating that the reaction requires one proton. On the other hand, kinetics of peroxynitrite isomerization catalyzed by ferric Ma-Pgb* (Ma-Pgb*-Fe(III is monophasic and values of the second order rate constant for peroxynitrite isomerization by Ma-Pgb*-Fe(III and of the first order rate constant for the spontaneous conversion of peroxynitrite to nitrate are h(app = 3.8 × 10(4 M(-1 s(-1 and h0 = 2.8 × 10(-1 s(-1 (at pH 7.4 and 20 °C. The pH-dependence of hon and h0 values reflects the acid-base equilibrium of peroxynitrite (pKa = 6.7 and 6.9, respectively; at 20 °C, indicating that HOONO is the species that reacts preferentially with the heme-Fe(III atom. These results highlight the potential role of Pgbs in the biosynthesis and scavenging of reactive nitrogen and oxygen species.

  16. Promotion of selective pathways in isomerizing functionalization of plant oils by rigid framework substituents

    KAUST Repository

    Christl, Josefine T.

    2014-10-14

    The 1,2-(CH2P(1-adamantyl)2)2C6H4 (dadpx) coordinated palladium complex [(dadpx)Pd(OTf)2] (1) is a catalyst precursor for the isomerizing methoxycarbonylation of the internal double bond of methyl oleate, with an unprecedented selectivity (96%) for the linear diester 1,19-dimethyl nonadecanedioate. Rapid formation of the catalytically active solvent-coordinated hydride species [(dadpx)PdH(MeOH)]+ (3-MeOH) is evidenced by NMR spectroscopy, and further isolation and X-ray crystal structure analysis of [(dadpx)PdH(PPh3)]+ (3-PPh3). DFT calculations of key steps of the catalytic cycle unravel methanolysis as the decisive step for enhanced selectivity and the influence of the rigid adamantyl framework on this step by destabilization of transition states of unselective pathways.

  17. Characterization of Isomeric Glycans by Reversed Phase Liquid Chromatography-Electronic Excitation Dissociation Tandem Mass Spectrometry

    Science.gov (United States)

    Tang, Yang; Wei, Juan; Costello, Catherine E.; Lin, Cheng

    2018-04-01

    The occurrence of numerous structural isomers in glycans from biological sources presents a severe challenge for structural glycomics. The subtle differences among isomeric structures demand analytical methods that can provide structural details while working efficiently with on-line glycan separation methods. Although liquid chromatography-tandem mass spectrometry (LC-MS/MS) is a powerful tool for mixture analysis, the commonly utilized collision-induced dissociation (CID) method often does not generate a sufficient number of fragments at the MS2 level for comprehensive structural characterization. Here, we studied the electronic excitation dissociation (EED) behaviors of metal-adducted, permethylated glycans, and identified key spectral features that could facilitate both topology and linkage determinations. We developed an EED-based, nanoscale, reversed phase (RP)LC-MS/MS platform, and demonstrated its ability to achieve complete structural elucidation of up to five structural isomers in a single LC-MS/MS analysis. [Figure not available: see fulltext.

  18. Antifungal activity and isomerization of octadecyl p-coumarates from Ipomoea carnea subsp. fistulosa.

    Science.gov (United States)

    Nidiry, Eugene Sebastian J; Ganeshan, Girija; Lokesha, Ankanahalli N

    2011-12-01

    Bioassay monitored HPLC assisted isolation and purification of the chief antifungal fraction of the leaves of Ipomoea carnea subsp. fistulosa (Convulvulaceae) were achieved using Colletotrichum gloeosporioides and Cladosporium cucumerinum as test organisms. The activity of the purified fraction was further confirmed by the dose dependent inhibition of the spore germination of Alternaria alternata and A. porri. The active fraction was identified as a mixture of (E)-octadecyl p-coumarate and (Z)-octadecyl p-coumarate. The two isomers were detected on an HPLC column with substantially different retention times, but once eluted from the column, one form was partly converted to the other in daylight. Conclusive evidence for the structures and their isomerization were obtained from the HPLC behavior, IR, UV, HRESIMS, CIMS and and NMR spectral data. Important 1H NMR and 13C NMR signals could be separately assigned for the isomers using 2D NMR techniques.

  19. Analysis of carboxylate coordination function of the isomeric lanthanide pyridinedicarboxylates by means of vibration spectroscopy

    International Nuclear Information System (INIS)

    Puntus, L.; Zolin, V.; Kudryashova, V.

    2004-01-01

    The investigation of IR spectra of salts of six isomers of pyridinedicarboxylic acid (PDA): 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-pyridinedicarboxylic acids, have demonstrated that properties of these salts are dependent on the bonding manner of carboxylate groups and on coordination of heterocyclic nitrogen atom. The most prominent differences in properties and spectra of 2,6- and 3,4-PDA salts are conditioned correspondingly by monodentate and bidentate coordination functions of the carboxylate groups in these compounds. The correlation of the breathing vibration frequency, reflecting the rigidity of the heterocyclic ring, with position of the carboxylate substituents, conditioning intramolecular charge transfer (CT), was postulated and proved by shifts of the breathing vibration frequency dependent on the structure of isomeric ligand

  20. Isomerization of butene-1 on rare earth oxides. [Rare earths: La, Nd, Dy

    Energy Technology Data Exchange (ETDEWEB)

    Khodakov, Yu S; Nesterov, V K; Minachev, Kh M [AN SSSR, Moscow. Inst. Organicheskoj Khimii

    1975-09-01

    A study has been made into the isomerization of butene-1 on oxides of rare-earth elements. The dependence of the reaction rate at 20/sup 0/C on the baking temperature of La and Nd oxides have the maximum at 700/sup 0/C. A decrease in the activity of these oxides after bakinq at 800/sup 0/C is observed, as well as during experiments at -30 deq C. In the case of Dy/sub 2/O/sub 3/, the activity at 20/sup 0/C increases gradually with Tsub(bak)=500 to 800/sup 0/C Zeolite 0.57LaNaY exhibits maximum activity at Tsub(bak)=500/sup 0/C Similar data as to the effect of the baking temperature on the catalyst activity were obtained earlier for hydrogenation of ethylene. According to their maximum activity, oxides of rare-earth elements, in the isomerization as well as hydrogenation reactions, can be arranged as follows: La/sub 2/O/sub 3/>Nd/sub 2/O/sub 3/

  1. High-Pressure Limit Rate Rules for α-H Isomerization of Hydroperoxyalkylperoxy Radicals

    KAUST Repository

    Mohamed, Samah Y

    2018-03-09

    Hydroperoxyalkylperoxy (OOQOOH) radical isomerization is an important low-temperature chain branching reaction within the mechanism of hydrocarbon oxidation. This isomerization may proceed via the migration of the α-hydrogen to the hydroperoxide group. In this work, a combination of high level composite methods - CBS-QB3, G3 and G4 - is used to determine the high-pressure-limit rate parameters for the title reaction. Rate rules for H-migration reactions proceeding through 5-, 6-, 7- and 8-membered ring transitions states are determined. Migrations from primary, secondary and tertiary carbon sites to the peroxy group are considered. Chirality is also investigated by considering two diastereomers for reactants and transition states with two chiral centers. This is important since chirality may influence the energy barrier of the reaction as well as the rotational energy barriers of hindered rotors in chemical species and transition states. The effect of chirality and hydrogen bonding interactions in the investigated energies and rate constants is studied. The results show that while the energy difference between two diastereomers ranges from 0.1 - 3.2 kcal, chirality hardly affects the kinetics, except at low temperatures (atmospheric conditions) or when two chiral centers are present in the reactant. Regarding the effects of the peroxy group position and the H-migration ring size, it is found that in most cases, the 1,5 and 1,6 H-migration reactions have similar rates at low temperatures (below ~830K) since the 1,6 H-migration proceeds via a cyclohexane-like transition state similar to that of the 1,5 H-migration.

  2. Interaction of slow neutrons with the second isomeric level Kπ=16+ of the 178Hf isotope

    International Nuclear Information System (INIS)

    Pangault, Laurence

    1999-01-01

    In this work, we study the interaction of low energy neutrons (E≤ 10 eV) with the second isomeric level of 178 Hf (l π =K π =16 + , T 1/2 =31 y) in (n,γ) reactions which proceed through the formation of a compound nucleus. The radiative decay of high K states in 179 Hf is investigated using an isomeric I π =16 + 178 Hf target, 40 ng in weight. The first experiment, performed at the high flux reactor in the Laue Langevin Institute in Grenoble, consisted in γ-ray spectroscopy measurements. For this purpose, an experimental set-up has been built. lt consists of four large Ge detectors shielded against background using a specific F 6 Li collimations ensemble. The second experiments performed at the Fakel (Kurchatov lnstitute, Moscow) and Gelina (IRMM Geel, Belgium) linear accelerators consisted in the investigation of neutron resonances in the 178 Hf m2 (n,γ) reaction using time of flight technique and their γ-decay paths. A high efficiency spectrometer has been built and used for the measurements at bath sites. Two resonances located at 1.82 eV and 0.75 eV have been observed and unambiguously assigned to the (n+ 178 Hf m2 ) compound system. The γ-decay properties of these resonances are very different. Furthermore, the γ-decay path followed by the 0.75 eV resonance is at odd with that expected form statistical model predictions. (author) [fr

  3. Cardiopulmonary Exercise Testing in Fontan Patients With and Without Isomerism (Heterotaxy) as Compared to Patients With Primary Ciliary Dyskinesia and Subjects With Structurally Normal Hearts

    DEFF Research Database (Denmark)

    Loomba, Rohit S; Danduran, Michael; Nielsen, Kim G

    2017-01-01

    with and without isomerism. We have now compared these finding with those from patients with primary ciliary dyskinesia, as many patients with isomerism have ciliary dyskinesia. We identified patients having the Fontan circulation with and without isomerism who had undergone cardiopulmonary exercise testing......, comparing the findings from healthy individuals undergoing exercise, and a comparable number of individuals with primary ciliary dyskinesia but no congenital heart disease. We were able to include a total of 68 patients in our study, with 17 in each of the four groups. Cardiopulmonary exercise testing...

  4. Compartmental and noncompartmental modeling of ¹³C-lycopene absorption, isomerization, and distribution kinetics in healthy adults.

    Science.gov (United States)

    Moran, Nancy E; Cichon, Morgan J; Riedl, Kenneth M; Grainger, Elizabeth M; Schwartz, Steven J; Novotny, Janet A; Erdman, John W; Clinton, Steven K

    2015-12-01

    Lycopene, which is a red carotenoid in tomatoes, has been hypothesized to mediate disease-preventive effects associated with tomato consumption. Lycopene is consumed primarily as the all-trans geometric isomer in foods, whereas human plasma and tissues show greater proportions of cis isomers. With the use of compartmental modeling and stable isotope technology, we determined whether endogenous all-trans-to-cis-lycopene isomerization or isomeric-bioavailability differences underlie the greater proportion of lycopene cis isomers in human tissues than in tomato foods. Healthy men (n = 4) and women (n = 4) consumed (13)C-lycopene (10.2 mg; 82% all-trans and 18% cis), and plasma was collected over 28 d. Unlabeled and (13)C-labeled total lycopene and lycopene-isomer plasma concentrations, which were measured with the use of high-performance liquid chromatography-mass spectrometry, were fit to a 7-compartment model. Subjects absorbed a mean ± SEM of 23% ± 6% of the lycopene. The proportion of plasma cis-(13)C-lycopene isomers increased over time, and all-trans had a shorter half-life than that of cis isomers (5.3 ± 0.3 and 8.8 ± 0.6 d, respectively; P lycopene bioavailability and endogenous trans-to-cis-lycopene isomerization was predictive of plasma (13)C and unlabeled cis- and all-trans-lycopene concentrations. Although the bioavailability of cis (24.5% ± 6%) and all-trans (23.2% ± 8%) isomers did not differ, endogenous isomerization (0.97 ± 0.25 μmol/d in the fast-turnover tissue lycopene pool) drove tissue and plasma isomeric profiles. (13)C-Lycopene combined with physiologic compartmental modeling provides a strategy for following complex in vivo metabolic processes in humans and reveals that postabsorptive trans-to-cis-lycopene isomerization, and not the differential bioavailability of isomers, drives tissue and plasma enrichment of cis-lycopene. This trial was registered at clinicaltrials.gov as NCT01692340. © 2015 American Society for Nutrition.

  5. Compartmental and noncompartmental modeling of 13C-lycopene absorption, isomerization, and distribution kinetics in healthy adults123

    Science.gov (United States)

    Moran, Nancy E; Cichon, Morgan J; Riedl, Kenneth M; Grainger, Elizabeth M; Schwartz, Steven J; Novotny, Janet A; Erdman, John W; Clinton, Steven K

    2015-01-01

    Background: Lycopene, which is a red carotenoid in tomatoes, has been hypothesized to mediate disease-preventive effects associated with tomato consumption. Lycopene is consumed primarily as the all-trans geometric isomer in foods, whereas human plasma and tissues show greater proportions of cis isomers. Objective: With the use of compartmental modeling and stable isotope technology, we determined whether endogenous all-trans-to-cis-lycopene isomerization or isomeric-bioavailability differences underlie the greater proportion of lycopene cis isomers in human tissues than in tomato foods. Design: Healthy men (n = 4) and women (n = 4) consumed 13C-lycopene (10.2 mg; 82% all-trans and 18% cis), and plasma was collected over 28 d. Unlabeled and 13C-labeled total lycopene and lycopene-isomer plasma concentrations, which were measured with the use of high-performance liquid chromatography–mass spectrometry, were fit to a 7-compartment model. Results: Subjects absorbed a mean ± SEM of 23% ± 6% of the lycopene. The proportion of plasma cis-13C-lycopene isomers increased over time, and all-trans had a shorter half-life than that of cis isomers (5.3 ± 0.3 and 8.8 ± 0.6 d, respectively; P lycopene bioavailability and endogenous trans-to-cis-lycopene isomerization was predictive of plasma 13C and unlabeled cis- and all-trans-lycopene concentrations. Although the bioavailability of cis (24.5% ± 6%) and all-trans (23.2% ± 8%) isomers did not differ, endogenous isomerization (0.97 ± 0.25 μmol/d in the fast-turnover tissue lycopene pool) drove tissue and plasma isomeric profiles. Conclusion: 13C-Lycopene combined with physiologic compartmental modeling provides a strategy for following complex in vivo metabolic processes in humans and reveals that postabsorptive trans-to-cis-lycopene isomerization, and not the differential bioavailability of isomers, drives tissue and plasma enrichment of cis-lycopene. This trial was registered at clinicaltrials.gov as NCT01692340. PMID

  6. The design of magnetic diagnostics for reconstructing of NCSX stellarator equilibria

    International Nuclear Information System (INIS)

    Lazarus, E.A.; Pomphrey, N.

    2005-01-01

    In previous work we have demonstrated that NCSX (National Compact Stellarator Experiment) will require active control of the helical and poloidal field coils in order to remain on a stable trajectory to high beta while retaining quasi-axisymmetry. We require a set of magnetic diagnostics that will be sensitive to changes in the equilibrium that represent departures from such a trajectory. That is, we will need to control features of the plasma boundary shape to a specification; that specification itself will vary with the current and pressure profiles. We need to determine a satisfactory set of magnetic sensors for this task To address this we have postulated a diagnostic set of 443 sensors that we believe is overly complete. A data base of ∼2500 free-boundary equilibria is created with variation of coil currents, plasma pressure and toroidal current profiles, plasma size, total pressure and total current. The signals expected on this array of diagnostics are calculated using a response function formalism. These are used in a linear regression to predict the magnetic field on a smallest vacuum surface that encompasses all the equilibria in the database. We have extended a standard 'variable selection' method of multivariate statistics to determine a complete ranking of the sensors. The ranking scheme is based on properties of the null space of the matrix of diagnostic signals for all equilibria in the database. Subsets are chosen according to this ranking and we judge adequacy by our ability to reconstruct the equilibrium with STELLOPT. While the ability to reconstruct the equilibrium in free boundary does not yield information on optimal control algorithms, it does show whether a particular set of sensors contains the necessary information to allow control of the plasma. Results will be reported. It is yet to be determined just how much information about the profiles can be known from external measurements. We will present results of a study that addresses this

  7. Free-Boundary 3D Equilibria and Resistive Wall Instabilities with Extended-MHD

    Science.gov (United States)

    Ferraro, N. M.

    2015-11-01

    The interaction of the plasma with external currents, either imposed or induced, is a critical element of a wide range of important tokamak phenomena, including resistive wall mode (RWM) stability and feedback control, island penetration and locking, and disruptions. A model of these currents may be included within the domain of extended-MHD codes in a way that preserves the self-consistency, scalability, and implicitness of their numerical methods. Such a model of the resistive wall and non-axisymmetric coils is demonstrated using the M3D-C1 code for a variety of applications, including RWMs, perturbed non-axisymmetric equilibria, and a vertical displacement event (VDE) disruption. The calculated free-boundary equilibria, which include Spitzer resistivity, rotation, and two-fluid effects, are compared to external magnetic and internal thermal measurements for several DIII-D discharges. In calculations of the perturbed equilibria in ELM suppressed discharges, the tearing response at the top of the pedestal is found to correlate with the onset of ELM suppression. Nonlinear VDE calculations, initialized using a vertically unstable DIII-D equilibrium, resolve in both space and time the currents induced in the wall and on the plasma surface, and also the currents flowing between the plasma and the wall. The relative magnitude of these contributions and the total impulse to the wall depend on the resistive wall time, although the maximum axisymmetric force on the wall over the course of the VDE is found to be essentially independent of the wall conductivity. This research was supported by US DOE contracts DE-FG02-95ER54309, DE-FC02-04ER54698 and DE-AC52-07NA27344.

  8. The prediction and representation of phase equilibria and physicochemical properties in complex coal ash slag systems

    Energy Technology Data Exchange (ETDEWEB)

    E. Jak; A. Kondratiev; S. Christie; P.C. Hayes [Centre for Coal in Sustainable Development (CCSD), Brisbane (Australia)

    2003-07-01

    A range of problems in coal utilisation technologies, including ash slag flow in slagging gasifiers, deposit formation, slagging, fouling, fusibility tests, fluxing, blending etc, are related to the melting behaviour of the mineral matter in the coal. To assist with solving these practical issues i) thermodynamic modelling of phase equilibria, and ii) viscosity modelling studies are being undertaken at the Pyrometallurgy Research Centre (The University of Queensland, Australia) with support from the Collaborative Research Centre for Coal in Sustainable Development (CCSD). The thermodynamic modelling has been carried out using the computer system FactSage, which is used for the calculation of multi-phase slag / solid / gas / matte / alloy / salt equilibria in multi-component systems of industrial interest. A modified quasi-chemical solution model is used for the liquid slag phase. New model optimisations have been carried out, which have significantly improved the accuracy of the thermodynamic models for coal combustion processes. Viscosity modelling, using a modified Urbain formalism, is carried out in conjunction with FactSage calculations to predict the viscosities of fully liquid as well as heterogeneous, partly crystallised slags. Custom designed software packages are developed using these fundamental models for wider use by industrial researchers and engineers, and for incorporation as process control modules. The new custom-designed computer software package can be used to produce limiting operability diagrams for slag systems. These diagrams are used to describe phase equilibria and physico-chemical properties in complex slag systems. The approach is illustrated with calculations on the system SiO{sub 2}-Al{sub 2}O{sub 3}-FeO-Fe{sub 2}O{sub 3}-CaO at metallic iron saturation, slags produced in coal slagging gasifiers. 28 refs., 7 figs., 1 tab.

  9. Is HO3 minimum cis or trans? An analytic full-dimensional ab initio isomerization path.

    Science.gov (United States)

    Varandas, A J C

    2011-05-28

    The minimum energy path for isomerization of HO(3) has been explored in detail using accurate high-level ab initio methods and techniques for extrapolation to the complete basis set limit. In agreement with other reports, the best estimates from both valence-only and all-electron single-reference methods here utilized predict the minimum of the cis-HO(3) isomer to be deeper than the trans-HO(3) one. They also show that the energy varies by less than 1 kcal mol(-1) or so over the full isomerization path. A similar result is found from valence-only multireference configuration interaction calculations with the size-extensive Davidson correction and a correlation consistent triple-zeta basis, which predict the energy difference between the two isomers to be of only Δ = -0.1 kcal mol(-1). However, single-point multireference calculations carried out at the optimum triple-zeta geometry with basis sets of the correlation consistent family but cardinal numbers up to X = 6 lead upon a dual-level extrapolation to the complete basis set limit of Δ = (0.12 ± 0.05) kcal mol(-1). In turn, extrapolations with the all-electron single-reference coupled-cluster method including the perturbative triples correction yield values of Δ = -0.19 and -0.03 kcal mol(-1) when done from triple-quadruple and quadruple-quintuple zeta pairs with two basis sets of increasing quality, namely cc-cpVXZ and aug-cc-pVXZ. Yet, if added a value of 0.25 kcal mol(-1) that accounts for the effect of triple and perturbative quadruple excitations with the VTZ basis set, one obtains a coupled cluster estimate of Δ = (0.14 ± 0.08) kcal mol(-1). It is then shown for the first time from systematic ab initio calculations that the trans-HO(3) isomer is more stable than the cis one, in agreement with the available experimental evidence. Inclusion of the best reported zero-point energy difference (0.382 kcal mol(-1)) from multireference configuration interaction calculations enhances further the relative

  10. Production cross sections and isomeric ratios for sup(110m)In/sup(110g)In formed in Cd (d,xn) reactions

    International Nuclear Information System (INIS)

    Herreros Usher, Oscar; Maceiras de Jefimowicz, Elena; De la Vega Vedoya, Mario; Jorge Nassiff, Sonia

    1980-01-01

    Excitation functions and isomeric cross sections ratios have been measured for the 110 Cd (d,2n) and 111 Cd (d,3n) reactions in which the isomeric pair sup(110m)In/sup(110g)In is produced. Activation method was employed and the irradiations were performed at the synchrocyclotron of the Comision Nacional de Energia Atomica, Argentina, with an incident energy of 27.MeV. (author) [es

  11. MOMCON: A spectral code for obtaining three-dimensional magnetohydrodynamic equilibria

    International Nuclear Information System (INIS)

    Hirshman, S.P.; Lee, D.K.

    1986-01-01

    A new code, MOMCON (spectral moments code with constraints), is described that computes three-dimensional ideal magnetohydrodynamic (MHD) equilibria in a fixed toroidal domain using a Fourier expansion for the inverse coordinates (R, Z) representing nested magnetic surfaces. A set of nonlinear coupled ordinary differential equations for the spectral coefficients of (R, Z) is solved using an accelerated steepest descent method. A stream function, lambda, is introduced to improve the mode convergence properties of the Fourier series for R and Z. The convergence rate of the R-Z spectra is optimized on each flux surface by solving nonlinear constraint equations relating the m>=2 spectral coefficients of R and Z. (orig.)

  12. Solid-liquid phase equilibria of Fe-Cr-Al alloys and spinels

    Science.gov (United States)

    McMurray, J. W.; Hu, R.; Ushakov, S. V.; Shin, D.; Pint, B. A.; Terrani, K. A.; Navrotsky, A.

    2017-08-01

    Ferritic FeCrAl alloys are candidate accident tolerant cladding materials. There is a paucity of data concerning the melting behavior for FeCrAl and its oxides. Analysis tools have therefore had to utilize assumptions for simulations using FeCrAl cladding. The focus of this study is to examine in some detail the solid-liquid phase equilibria of FeCrAl alloys and spinels with the aim of improving the accuracy of severe accident scenario computational studies.

  13. Phase equilibria of didecyldimethylammonium nitrate ionic liquid with water and organic solvents

    International Nuclear Information System (INIS)

    Domanska, Urszula; Lugowska, Katarzyna; Pernak, Juliusz

    2007-01-01

    The phase diagrams for binary mixtures of an ammonium ionic liquid, didecyldimethylammonium nitrate, [DDA][NO 3 ], with: alcohols (propan-1-ol, butan-1-ol, octan-1-ol, and decan-1-ol): hydrocarbons (toluene, propylbenzene, hexane, and hexadecane) and with water were determined in our laboratory. The phase equilibria were measured by a dynamic method from T 220 K to either the melting point of the ionic liquid, or to the boiling point of the solvent. A simple liquidus curve in a eutectic system was observed for [DDA][NO 3 ] with: alcohols (propan-1-ol, butan-1-ol, and octan-1-ol); aromatic hydrocarbons (toluene and propylbenzene) and with water. (Solid + liquid) equilibria with immiscibility in the liquid phase were detected with the aliphatic hydrocarbons heptane and hexadecane and with decan-1-ol. (Liquid + liquid) equilibria for the system [DDA][NO 3 ] with hexadecane was observed for the whole mole fraction range of the ionic liquid. The observation of the upper critical solution temperature in binary mixtures of ([DDA][NO 3 ] + decan-1-ol, heptane, or hexadecane) was limited by the boiling temperature of the solvent. Characterisation and purity of the compounds were determined by elemental analysis, water content (Fisher method) and differential scanning microcalorimetry (d.s.c.) analysis. The d.s.c. method of analysis was used to determine melting temperatures and enthalpies of fusion. The thermal stability of the ionic liquid was resolved by the thermogravimetric technique-differential thermal analysis (TG-DTA) technique over a wide temperature range from (200 to 780) K. The thermal decomposition temperature of 50% of the sample was greater than 500 K. The (solid + liquid) phase equilibria, curves were correlated by means of different G Ex models utilizing parameters derived from the (solid + liquid) equilibrium. The root-mean-square deviations of the solubility temperatures for all calculated data are dependent upon the particular system and the particular

  14. Sunspot Equilibria in a Production Economy: Do Rational Animal Spirits Cause Overproduction?

    OpenAIRE

    Kajii, Atsushi

    2008-01-01

    We study a standard two period economy with one nominal bond and one firm. The input of the firm is done in the first period and financed with the nominal bond, and its profits are distributed to the shareholders in the second period. We show that a sunspot equilibrium exists around each efficient equilibrium. The interest rate is lower than optimal and there is over production in sunspot equilibria, under some conditions. But a sunspot equilibrium does not exist if the profit share can be tr...

  15. Thermal analysis and prediction of phase equilibria in ternary Pb-Zn-Ag system

    Directory of Open Access Journals (Sweden)

    Živković D.

    2011-01-01

    Full Text Available Ternary Pb-Zn-Ag system is typical for some physicochemical processes going on in refining phase in the extractive metallurgy of lead. Therefore, investigation of mentioned system is important from both theoretical and practical research of the phenomena occurring during the lead desilverizing process. The results of experimental investigation using differential thermal analysis (DTA and thermodynamic calculation of phase equilibria in Pb-Zn-Ag system according to CALPHAD method, in the sections with Zn:Ag mass ratio equal to 90:10, 70:30 and 50:50, are presented in this paper.

  16. Multistep Hybrid Iterations for Systems of Generalized Equilibria with Constraints of Several Problems

    Directory of Open Access Journals (Sweden)

    Lu-Chuan Ceng

    2014-01-01

    Full Text Available We first introduce and analyze one multistep iterative algorithm by hybrid shrinking projection method for finding a solution of the system of generalized equilibria with constraints of several problems: the generalized mixed equilibrium problem, finitely many variational inclusions, the minimization problem for a convex and continuously Fréchet differentiable functional, and the fixed-point problem of an asymptotically strict pseudocontractive mapping in the intermediate sense in a real Hilbert space. We prove strong convergence theorem for the iterative algorithm under suitable conditions. On the other hand, we also propose another multistep iterative algorithm involving no shrinking projection method and derive its weak convergence under mild assumptions.

  17. Computed phase equilibria for burnable neutron absorbing materials for advanced pressurized heavy water reactors

    Energy Technology Data Exchange (ETDEWEB)

    Corcoran, E.C. [Department of Chemistry and Chemical Engineering, Royal Military College of Canada, P.O. Box 17000, St. Forces, Kingston, Ont., K7K 7B4 (Canada)], E-mail: emily.corcoran@rmc.ca; Lewis, B.J.; Thompson, W.T. [Department of Chemistry and Chemical Engineering, Royal Military College of Canada, P.O. Box 17000, St. Forces, Kingston, Ont., K7K 7B4 (Canada); Hood, J. [Atomic Energy of Canada Ltd., Sheridan Park, 2251 Speakman Drive, Mississauga, Ont., L5K 1B2 (Canada); Akbari, F.; He, Z. [Atomic Energy of Canada Ltd., Chalk River Laboratories, Chalk River, Ont., K0J 1J0 (Canada); Reid, P. [Atomic Energy of Canada Ltd., Sheridan Park, 2251 Speakman Drive, Mississauga, Ont., L5K 1B2 (Canada)

    2009-03-31

    Burnable neutron absorbing materials are expected to be an integral part of the new fuel design for the Advanced CANDU [CANDU is as a registered trademark of Atomic Energy of Canada Limited.] Reactor. The neutron absorbing material is composed of gadolinia and dysprosia dissolved in an inert cubic-fluorite yttria-stabilized zirconia matrix. A thermodynamic model based on Gibbs energy minimization has been created to provide estimated phase equilibria as a function of composition and temperature. This work includes some supporting experimental studies involving X-ray diffraction.

  18. Representing Strategic Games and Their Equilibria in Many-Valued Logics

    Czech Academy of Sciences Publication Activity Database

    Běhounek, Libor; Cintula, Petr; Fermüller, C.; Kroupa, Tomáš

    2016-01-01

    Roč. 24, č. 3 (2016), s. 238-267 ISSN 1367-0751 R&D Projects: GA ČR GAP402/12/1309; GA MŠk 7AMB13AT014; GA ČR(CZ) GF15-34650L Grant - others:Austrian Science Fund(AT) P25417-G15; Austrian Science Fund(AT) I1897-N25 Institutional support: RVO:67985807 ; RVO:67985556 Keywords : strategic games * many-valued logics * Nash equilibria * Lukasiewicz games Subject RIV: BA - General Mathematics Impact factor: 0.575, year: 2016

  19. Experimental determination and prediction of liquid-solid equilibria for binary (methyl palimitate + naphthalene mixture

    Directory of Open Access Journals (Sweden)

    Benziane M.

    2013-07-01

    Full Text Available Solid-liquid equilibria for binary mixtures of {Methyl palmitate (1 + Naphthalene (2} were measured using differential scanning calorimeter (DSC. Simple eutectic behaviours for this system are observed. The experimental results were correlated by means of the NRTL, Wilson, UNIQUAC and ideal models. The root-mean-square deviations of the solubility temperatures for all measured data vary from 0.5477 K (for UNIQUAC model to 3.34K; the deviation depend on the model used. The best solubility correlation was obtained with UNIQUAC model and this observation confirms previous results.

  20. Ion-molecular equilibria and activity determination in the RbF-ZrF4 system

    International Nuclear Information System (INIS)

    Skokan, E.V.; Nikitin, M.I.; Sorokin, I.D.; Korenev, Yu.M.; Sidorov, L.N.

    1983-01-01

    Activity of zirconium tetrofluoride in 100-33.3 mol % ZrF 4 concentration range was determined during isothermal evaporation of samples of different initial composition of RbF-ZrF 4 system, using ion-molecular equilibrium method. It became possible, using the exchange ion-molecular reactions to determine ZrF 4 activity approximately 10 -10 in the region of state diagram of RbF-ZrF 4 system, adjoining to rubidium fluoride. The comparative analysis of results, obtained by the methods of isothermal evaporation, ion-molecular equilibria is given; the advantages and restrictions of ion-molecular equilibrium method are presented

  1. Equilibria of a Two-Person Non-Zerosum Noisy Game of Timing,

    Science.gov (United States)

    1981-01-01

    AD-A097 158 YALE UNIV NEW HAVEN CT COWLES FOUNDATION FOR RESEARC -ETC F/B 12/1 EQUILIBRIA OF A TWO-PERSON ON-ZEROSUN OISY GAME OF TIMING, CUb .JAN al...pubUo zeleale Distribution Unlimited. 1. Introduction Two toothpaste manufacturers are competing for a larger share of the dentifrice market . Each is...successfully capturing a share of the market , if its product hits the stores first. (This is assuming that the toothpaste is being technologically

  2. Computation of zero. beta. three-dimensional equilibria with magnetic islands

    Energy Technology Data Exchange (ETDEWEB)

    Reiman, A.H.; Greenside, H.S.

    1989-01-01

    A Picard iteration scheme has been implemented for the computation of toroidal, fully three-dimensional, zero ..beta.. equilibria with islands and stochastic regions. Representation of the variables in appropriate coordinate systems has been found to be a key to making the scheme work well. In particular, different coordinate systems are used for solving magnetic differential equations and Ampere's law. The current profile is adjusted when islands and stochastic regions appear. An underrelaxation of the current profile modifications is generally needed for stable iteration of the algorithm. Some examples of equilibrium calculations are presented. 16 refs., 6 figs., 1 tab.

  3. Truth-telling and Nash equilibria in minimum cost spanning tree models

    DEFF Research Database (Denmark)

    Hougaard, Jens Leth; Tvede, Mich

    2012-01-01

    In this paper we consider the minimum cost spanning tree model. We assume that a central planner aims at implementing a minimum cost spanning tree not knowing the true link costs. The central planner sets up a game where agents announce link costs, a tree is chosen and costs are allocated according...... to the rules of the game. We characterize ways of allocating costs such that true announcements constitute Nash equilibria both in case of full and incomplete information. In particular, we find that the Shapley rule based on the irreducible cost matrix is consistent with truthful announcements while a series...

  4. Phase equilibria in Dy-Cu-Al system at 500 deg C

    International Nuclear Information System (INIS)

    Kuz'ma, Yu.B.; Milyan, V.V.

    1989-01-01

    Using the methods of X-ray diffraction analysis a diagram of phase equilibria in Dy-Cu-Al system at 500 deg C is plotted. Boundaries of solid solutions on the basis of DyCu 2 , DyCu and DyAl 2 compounds are determined and homogeneity regions of ternary compounds Dy 2 (Cu, Al) 7 and Dy(CuAl) 5 are ascertained. Compounds DyCuAl 3 , Dy 4 Cu 4 Al 11 and Dy 5 Cu 6 Al 9 have been detected for the first time

  5. Elastic energy and metastable phase equilibria for coherent mixtures in cubic systems

    International Nuclear Information System (INIS)

    Williams, R.O.

    1979-02-01

    Expressions were derived for the elastic energy due to coherency for cubic systems for an isotropic structure and for (100) or (111) habit planes for a lamellar structure. For the metastable equilibria the usual tangent compositions are replaced by compositions that are tangent to the elastic energy curve. For a loss of coherency there is an energy decrease due to the elastic effects and a further decrease associated with compositional changes. Information contained within this treatment permits calculation of the x-ray diffraction effects for such structures

  6. Simulation of Chemical Reaction Equilibria by the Reaction Ensemble Monte Carlo Method:

    Czech Academy of Sciences Publication Activity Database

    Turner, C.H.; Brennan, J.K.; Lísal, Martin; Smith, W.R.; Johnson, J. K.; Gubbins, K.E.

    2008-01-01

    Roč. 34, č. 2 (2008), s. 119-146 ISSN 0892-7022 R&D Projects: GA AV ČR KAN400720701; GA ČR GA203/05/0725; GA AV ČR IAA400720710; GA AV ČR 1ET400720507 Grant - others:NRCC(CA) OGP1041 Institutional research plan: CEZ:AV0Z40720504 Keywords : simulation * review * reaction equilibria Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.325, year: 2008

  7. Thermal solid-state Z/E isomerization of 2-alkylidene-4-oxothiazolidines: effects of non-covalent interactions

    Directory of Open Access Journals (Sweden)

    ZDRAVKO DŽAMBASKI

    2011-03-01

    Full Text Available Configurational isomerization of stereo-defined 5-substituted and unsubstituted 2-alkylidene-4-oxothiazolidines (1 in the solid state, giving the Z/E mixtures in various ratios, was investigated by 1H-NMR spectroscopy, X-ray powder crystallography and differential scanning calorimetry (DSC. The Z/E composition can be rationalized in terms of non-covalent interactions, involving intermolecular and intramolecular hydrogen bonding and directional non-bonded 1,5-type S×××O interactions. X-Ray powder crystallography, using selected crystalline (Z-4-oxothiazolidine substrates, revealed transformation to the amorphous state during the irreversible Z®E process. A correlation between previous results on the Z/E isomerization in solution and now in the solid state was established.

  8. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    Science.gov (United States)

    Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

    2016-07-01

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N2, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  9. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    International Nuclear Information System (INIS)

    Justino, Licínia L. G.; Reva, Igor; Fausto, Rui

    2016-01-01

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N 2 , Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  10. Investigating the large deformation of the 5 /2+ isomeric state in 73Zn: An indicator for triaxiality

    Science.gov (United States)

    Yang, X. F.; Tsunoda, Y.; Babcock, C.; Billowes, J.; Bissell, M. L.; Blaum, K.; Cheal, B.; Flanagan, K. T.; Garcia Ruiz, R. F.; Gins, W.; Gorges, C.; Grob, L. K.; Heylen, H.; Kaufmann, S.; Kowalska, M.; Krämer, J.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Otsuka, T.; Papuga, J.; Sánchez, R.; Wraith, C.; Xie, L.; Yordanov, D. T.

    2018-04-01

    Recently reported nuclear spins and moments of neutron-rich Zn isotopes measured at ISOLDE-CERN [C. Wraith et al., Phys. Lett. B 771, 385 (2017), 10.1016/j.physletb.2017.05.085] show an uncommon behavior of the isomeric state in 73Zn. Additional details relating to the measurement and analysis of the Znm73 hyperfine structure are addressed here to further support its spin-parity assignment 5 /2+ and to estimate its half-life. A systematic investigation of this 5 /2+ isomer indicates that significant collectivity appears due to proton/neutron E 2 excitations across the proton Z = 28 and neutron N = 50 shell gaps. This is confirmed by the good agreement of the observed quadrupole moments with large scale Monte Carlo shell model calculations. In addition, potential energy surface calculations in combination with T plots reveal a triaxial shape for this isomeric state.

  11. Retrieving molecular structural information and tracking HNC/HCN isomerization process with high harmonic generation by ultrashort laser pulses

    International Nuclear Information System (INIS)

    Nguyen Ngoc Ty; Le Van Hoang; Vu Ngoc Tuoc; Le Anh Thu

    2010-01-01

    We investigate the possibility of applying the iterative method, suggested in our previous work, for HCN molecule and its HNC isomer. We found that the high-order harmonic generation (HHG) spectra are quite insensitive to the change of H-C (or H-N) bond length so that only the inter-nuclear C-N distance can be retrieved from the high-order harmonic spectra using ultrashort intense lasers. Furthermore, by analyzing the HHG spectra emitted by HCN during the chemical reaction path of isomerization we identify the intensity peaks nearby the stable, metastable and transition states. this finding can be useful for tracking the HNC/HNC isomerization process. (author)

  12. Evidence for tunneling in base-catalyzed isomerization of glyceraldehyde to dihydroxyacetone by hydride shift under formose conditions.

    Science.gov (United States)

    Cheng, Liang; Doubleday, Charles; Breslow, Ronald

    2015-04-07

    Hydrogen atom transfer reactions between the aldose and ketose are key mechanistic features in formose chemistry by which formaldehyde is converted to higher sugars under credible prebiotic conditions. For one of these transformations, we have investigated whether hydrogen tunneling makes a significant contribution to the mechanism by examining the deuterium kinetic isotope effect associated with the hydrogen transfer during the isomerization of glyceraldehyde to the corresponding dihydroxyacetone. To do this, we developed a quantitative HPLC assay that allowed us to measure the apparent large intrinsic kinetic isotope effect. From the Arrhenius plot of the kinetic isotope effect, the ratio of the preexponential factors AH/AD was 0.28 and the difference in activation energies Ea(D) - Ea(H) was 9.1 kJ·mol(-1). All these results imply a significant quantum-mechanical tunneling component in the isomerization mechanism. This is supported by multidimensional tunneling calculations using POLYRATE with small curvature tunneling.

  13. Results of a Direct Search Using Synchrotron Radiation for the Low-Energy (229)Th Nuclear Isomeric Transition.

    Science.gov (United States)

    Jeet, Justin; Schneider, Christian; Sullivan, Scott T; Rellergert, Wade G; Mirzadeh, Saed; Cassanho, A; Jenssen, H P; Tkalya, Eugene V; Hudson, Eric R

    2015-06-26

    We report the results of a direct search for the (229)Th (I(π)=3/2(+)←5/2(+)) nuclear isomeric transition, performed by exposing (229)Th-doped LiSrAlF(6) crystals to tunable vacuum-ultraviolet synchrotron radiation and observing any resulting fluorescence. We also use existing nuclear physics data to establish a range of possible transition strengths for the isomeric transition. We find no evidence for the thorium nuclear transition between 7.3 eV and 8.8 eV with transition lifetime (1-2) s≲τ≲(2000-5600)  s. This measurement excludes roughly half of the favored transition search area and can be used to direct future searches.

  14. Thermally and vibrationally induced conformational isomerizations, infrared spectra, and photochemistry of gallic acid in low-temperature matrices

    Energy Technology Data Exchange (ETDEWEB)

    Justino, Licínia L. G., E-mail: liciniaj@ci.uc.pt; Reva, Igor; Fausto, Rui [CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra (Portugal)

    2016-07-07

    Near-infrared (near-IR) narrowband selective vibrational excitation and annealing of gallic acid (3,4,5-trihydroxybenzoic acid) isolated in cryogenic matrices were used to induce interconversions between its most stable conformers. The isomerizations were probed by infrared spectroscopy. An extensive set of quantum chemical calculations, carried out at the DFT(B3LYP)/6-311++G(d,p) level of approximation, was used to undertake a detailed analysis of the ground state potential energy surface of the molecule. This investigation of the molecule conformational space allowed extracting mechanistic insights into the observed annealing- or near-IR-induced isomerization processes. The infrared spectra of the two most stable conformers of gallic acid in N{sub 2}, Xe, and Ar matrices were fully assigned. Finally, the UV-induced photochemistry of the matrix isolated compound was investigated.

  15. DFT study on the isomerization and tautomerism in vitamins B3 (niacin), B5 (pantothenic acid) and B7 (biotin)

    Science.gov (United States)

    Valadbeigi, Younes; Farrokhpour, Hossein; Tabrizchi, Mahmoud

    2014-05-01

    Isomerization and tautomerism of the three water soluble vitamins including B3, B5 and B7 were studied applying density functional theory using B3LYP method in gas and aqueous phases. Activation energies (Ea), Gibbs free energies of activation (ΔG#), and imaginary frequencies of the transition state structures were calculated for all the isomerization and tautomerism reactions. Activation energies of the neutral → zwitterion (amine-enamine) tautomerism in vitamin B3 were 310-360 kJ/mol where these values for the keto-enol tautomerism were 100-130 kJ/mol. It was found that water molecule catalyzes the tautomerism and decreases the activation energies about 90-160 kJ/mol.

  16. Activation cross section and isomeric cross section ratios for the (n ,2 n ) reaction on 153Eu

    Science.gov (United States)

    Luo, Junhua; Jiang, Li; Li, Suyuan

    2017-10-01

    The 153Eu(n ,2 n ) m1,m2,g152Eu cross section was measured by means of the activation technique at three neutron energies in the range 13-15 MeV. The quasimonoenergetic neutron beam was formed via the 3H(d ,n ) 4He reaction, in the Pd-300 Neutron Generator at the Chinese Academy of Engineering Physics (CAEP). The activities induced in the reaction products were measured using high-resolution γ-ray spectroscopy. The cross section of the population of the second high-spin (8-) isomeric state was measured along with the reaction cross section populating both the ground (3-) and the first isomeric state (0-). Cross sections were also evaluated theoretically using the numerical code TALYS-1.8, with different level density options at neutron energies varying from the reaction threshold to 20 MeV. Results are discussed and compared with the corresponding literature.

  17. Phase equilibria for mixtures containing very many components. development and application of continuous thermodynamics for chemical process design

    International Nuclear Information System (INIS)

    Cotterman, R.L.; Bender, R.; Prausnitz, J.M.

    1984-01-01

    For some multicomponent mixtures, where detailed chemical analysis is not feasible, the compositio of the mixture may be described by a continuous distribution function of some convenient macroscopic property suc as normal boiling point or molecular weight. To attain a quantitative description of phase equilibria for such mixtures, this work has developed thermodynamic procedures for continuous systems; that procedure is called continuous thermodynamics. To illustrate, continuous thermodynamics is used to calculate dew points for natural-gas mixtures, solvent loss in a high-pressure absorber, and liquid-liquid phase equilibria in a polymer fractionation process. Continuous thermodynamics provides a rational method for calculating phase equilibria for those mixtures where complete chemical analysis is not available but where composition can be given by some statistical description. While continuous thermodynamics is only the logical limit of the well-known pseudo-component method, it is more efficient than that method because it is less arbitrary and it often requires less computer time

  18. Calculation of ethanol refining by means of extractive distillation with water using simulated data on phase equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Rosak, J; Mertl, I; Huml, M; Wichterle, I

    1980-01-01

    Available data on phase equilibria in binary mixtures pertaining to the system ethanol - water - impurities (7 compounds that represent the main impurities present in raw synthetic or fermentation ethanol) have been gathered for the computer calculation of a column to be used for the refining of ethanol. Missing experimental data on phase equilibria were supplied by simulation using the increment method UNIFAC which predicts phase equilibria on the basis of the chemical structure. All data about the behavior of binary mixtures were correlated by means of the NRTL method and the sets of constants thus obtained were then used in calculations of the column for the refining of ethanol. The results were compared with reality verified on industrial scale.

  19. Isomerization and Fragmentation of Cyclohexanone in a Heated Micro-Reactor.

    Science.gov (United States)

    Porterfield, Jessica P; Nguyen, Thanh Lam; Baraban, Joshua H; Buckingham, Grant T; Troy, Tyler P; Kostko, Oleg; Ahmed, Musahid; Stanton, John F; Daily, John W; Ellison, G Barney

    2015-12-24

    The thermal decomposition of cyclohexanone (C6H10═O) has been studied in a set of flash-pyrolysis microreactors. Decomposition of the ketone was observed when dilute samples of C6H10═O were heated to 1200 K in a continuous flow microreactor. Pyrolysis products were detected and identified by tunable VUV photoionization mass spectroscopy and by photoionization appearance thresholds. Complementary product identification was provided by matrix infrared absorption spectroscopy. Pyrolysis pressures were roughly 100 Torr, and contact times with the microreactors were roughly 100 μs. Thermal cracking of cyclohexanone appeared to result from a variety of competing pathways, all of which open roughly simultaneously. Isomerization of cyclohexanone to the enol, cyclohexen-1-ol (C6H9OH), is followed by retro-Diels-Alder cleavage to CH2═CH2 and CH2═C(OH)-CH═CH2. Further isomerization of CH2═C(OH)-CH═CH2 to methyl vinyl ketone (CH3CO-CH═CH2, MVK) was also observed. Photoionization spectra identified both enols, C6H9OH and CH2═C(OH)-CH═CH2, and the ionization threshold of C6H9OH was measured to be 8.2 ± 0.1 eV. Coupled cluster electronic structure calculations were used to establish the energetics of MVK. The heats of formation of MVK and its enol were calculated to be ΔfH298(cis-CH3CO-CH═CH2) = -26.1 ± 0.5 kcal mol(-1) and ΔfH298(s-cis-1-CH2═C(OH)-CH═CH2) = -13.7 ± 0.5 kcal mol(-1). The reaction enthalpy ΔrxnH298(C6H10═O → CH2═CH2 + s-cis-1-CH2═C(OH)-CH═CH2) is 53 ± 1 kcal mol(-1) and ΔrxnH298(C6H10═O → CH2═CH2 + cis-CH3CO-CH═CH2) is 41 ± 1 kcal mol(-1). At 1200 K, the products of cyclohexanone pyrolysis were found to be C6H9OH, CH2═C(OH)-CH═CH2, MVK, CH2CHCH2, CO, CH2═C═O, CH3, CH2═C═CH2, CH2═CH-CH═CH2, CH2═CHCH2CH3, CH2═CH2, and HC≡CH.

  20. Thiyl radical-induced cis-trans-isomerization of arachidonic acid inhibits prostaglandin metabolism

    International Nuclear Information System (INIS)

    Kratzsch, S.; Droessler, K.; Sprinz, H.; Brede, O.

    2002-01-01

    Complete text of publication follows. Thiyl radicals radiolytically generated from thiophenol in methanolic solution are known to isomerise double bonds of poly-unsaturated fatty acids (PUFA). γ-irradiating of such a system containing all-cis 5,8,11,14 eicosatetraenoic acid (arachidonic acid, AA) with low doses (0.1-0.8 kGy) results in a mixture of 8 to 32% mono-trans-isomers. Here we report about the influence of mono-trans-AA on the primary steps of AA-metabolism and prostaglandin synthesis, catalysed by cyclooxygenase (COX). In the cell-free model system the reaction of COX-1 with AA was analysed by controlling the oxygen level during the enzymatic reaction. As an example, a mixture of a low quantity of mono-trans-isomerized AA (10%) and 90% all-cis-isomer exhibits a marked reduced oxygen consumption by 45%. As further proofs - the yield of reactive oxygen species (ROS) generated by the COX-coupled peroxidase reaction was detected, - and the COX-1 activity in presence of different amounts of trans-AA was characterized using a photometric assay based on the oxidation of TMPD. All these methods indicated semiquantitatively a reduced activity of COX-1, depending on the trans-isomer yield. Therefore, an inhibition of COX-1 activity by only one trans-double-bond in AA could be concluded. Furthermore, in vitro cell-line experiments were performed analysing the influence of mono-trans-isomerized AA on the activity of the cell-own COX-2. Hence, VD 3 -differentiated and LPS-stimulated monocyte-like cells were incubated with mono-trans-AA and ROS-production was detected by the chemiluminescence measurements mentioned above. Compared to the reaction with all-cis-AA we found a considerable lowered formation of ROS. Likewise, we obtained a reduced PGE 2 -expression between 15 and 40% for cells treated with 8 to 29% trans-AA. The model as well as in vivo experiments demonstrate an inhibition effect of mono-trans-AA and give rise for postulating an enzyme blocking mechanism

  1. Biosynthesis of monoterpenes: Stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes

    International Nuclear Information System (INIS)

    Croteau, R.; Gershenzon, J.; Wheeler, C.J.; Satterwhite, D.M.

    1990-01-01

    The conversion of geranyl pyrophosphate to (+)-bornyl pyrophosphate and (+)-camphene is considered to proceed by the initial isomerization of the substrate to (-)-(3R)-linalyl pyrophosphate and the subsequent cyclization of this bound intermediate. In the case of (-)-bornyl pyrophosphate and (-)-camphene, isomerization of the substrate to the (+)-(3S)-linalyl intermediate precedes cyclization. The geranyl and linalyl precursors were shown to be mutually competitive substrates (inhibitors) of the relevant cyclization enzymes isolated from Salvia officinalis (sage) and Tanacetum vulgare (tansy) by the mixed substrate analysis method, demonstrating that isomerization and cyclization take place at the same active site. Incubation of partially purified enzyme preparations with (3R)-[1Z-3H]linalyl pyrophosphate plus [1-14C]geranyl pyrophosphate gave rise to double-labeled (+)-bornyl pyrophosphate and (+)-camphene, whereas incubation of enzyme preparations catalyzing the antipodal cyclizations with (3S)-[1Z-3H]-linalyl pyrophosphate plus [1-14C]geranyl pyrophosphate yielded double-labeled (-)-bornyl pyrophosphate and (-)-camphene. Each product was then transformed to the corresponding (+)- or (-)-camphor without change in the 3H:14C isotope ratio, and the location of the tritium label was deduced in each case by stereoselective, base-catalyzed exchange of the exo-alpha-hydrogen of the derived ketone. The finding that the 1Z-3H of the linalyl precursor was positioned at the endo-alpha-hydrogen of the corresponding camphor in all cases, coupled to the previously demonstrated retention of configuration at C1 of the geranyl substrate in these transformations, confirmed the syn-isomerization of geranyl pyrophosphate to linalyl pyrophosphate and the cyclization of the latter via the anti,endo- conformer

  2. Comparison of Separation of Seed Oil Triglycerides Containing Isomeric Conjugated Octadecatrienoic Acid Moieties by Reversed-Phase HPLC

    OpenAIRE

    Anh Van Nguyen; Victor Deineka; Lumila Deineka; Anh Vu Thi Ngoc

    2017-01-01

    Relative retention analysis and increment approach were applied for the comparison of triglycerides (TGs) retention of a broad set of plant seed oils with isomeric conjugated octadecatrienoic acids (CLnA) by reversed-phase HPLC for “propanol-2-acetonitrile” mobile phases and Kromasil 100-5C18 stationary phase with diode array detection (DAD) and mass spectrometric (MS) detection. The subjects of investigation were TGs of seed oils: Calendula officinalis, Catalpa ovata, Jacaranda mimosifolia, ...

  3. Stability constants of mixed ligand complexes of dioxouranium(II) and thorium(IV) with complexones and isomeric alanines

    International Nuclear Information System (INIS)

    Singh, R.K.; Saxena, M.C.

    1992-01-01

    The present work reports on the stability sequence between UO 2 II and Th IV ions for their mixed ligands complexes with the two isomeric alanines, α-alanine (α-ala) and β-alanine (β-ala) containing a complexone as primary ligand. The complexones used are iminodiacetate (IMDA), nitrilotricetate (NTA), 2-hydroxyethylenediaminetriacetate (HEDTA), ethylenediaminetetraacetate (EDTA), 1,2-diaminocyclohexanetraacetate (CDTA) and diethylenetriminepentaacetate (DTPA). (author). 9 refs., 1 tab

  4. Hydro-isomerization of n-hexane on bi-functional catalyst: Effect of total and hydrogen partial pressures

    Science.gov (United States)

    Thoa, Dao Thi Kim; Loc, Luu Cam

    2017-09-01

    The effect of both total pressure and hydrogen partial pressure during n-hexane hydro-isomerization over platinum impregnated on HZSM-5 was studied. n-Hexane hydro-isomerization was conducted at atmospheric pressure and 0.7 MPa to observe the influence of total pressure. In order to see the effect of hydrogen partial pressure, the reaction was taken place at different partial pressure of hydrogen varied from 307 hPa to 718 hPa by dilution with nitrogen to keep the total pressure at 0.1 MPa. Physico-chemical characteristics of catalyst were determined by the methods of nitrogen physi-sorption BET, SEM, XRD, TEM, NH3-TPD, TPR, and Hydrogen Pulse Chemi-sorption. Activity of catalyst in the hydro-isomerization of n-hexane was studied in a micro-flow reactor in the temperature range of 225-325 °C; the molar ratio H2/ hydrocarbon: 5.92, concentration of n-hexane: 9.2 mol.%, GHSV 2698 h-1. The obtained catalyst expressed high acid density, good reducing property, high metal dispersion, and good balance between metallic and acidic sites. It is excellent contact for n-hexane hydro-isomerization. At 250 °C, n-hexane conversion and selectivity were as high as 59-76 % and 85-99 %, respectively. It was found that catalytic activity was promoted either by total pressure or hydrogen partial pressure. At total pressure of 0.7 MPa while hydrogen partial pressure of 718 hPa, catalyst produced 63 RON liquid product containing friendly environmental iso-paraffins which is superior blending stock for green gasoline. Hydrogen did not only preserve catalyst actives by depressing hydrocracking and removing coke precursors but also facilitated hydride transfer step in the bi-functional bi-molecular mechanism.

  5. The introduction of hydrogen bond and hydrophobicity effects into the rotational isomeric states model for conformational analysis of unfolded peptides

    Science.gov (United States)

    Engin, Ozge; Sayar, Mehmet; Erman, Burak

    2009-03-01

    Relative contributions of local and non-local interactions to the unfolded conformations of peptides are examined by using the rotational isomeric states model which is a Markov model based on pairwise interactions of torsion angles. The isomeric states of a residue are well described by the Ramachandran map of backbone torsion angles. The statistical weight matrices for the states are determined by molecular dynamics simulations applied to monopeptides and dipeptides. Conformational properties of tripeptides formed from combinations of alanine, valine, tyrosine and tryptophan are investigated based on the Markov model. Comparison with molecular dynamics simulation results on these tripeptides identifies the sequence-distant long-range interactions that are missing in the Markov model. These are essentially the hydrogen bond and hydrophobic interactions that are obtained between the first and the third residue of a tripeptide. A systematic correction is proposed for incorporating these long-range interactions into the rotational isomeric states model. Preliminary results suggest that the Markov assumption can be improved significantly by renormalizing the statistical weight matrices to include the effects of the long-range correlations.

  6. Light-induced linkage isomerization of photochromic [Ru(bpy){sub 2}(R-OSO)]{sup +} compounds

    Energy Technology Data Exchange (ETDEWEB)

    Springfeld, Kristin; Dieckmann, Volker; Eicke, Sebastian; Imlau, Mirco [Department of Physics, University of Osnabrueck (Germany); Rack, Jeffrey J. [Department of Chemistry and Biochemistry, Ohio University, Athens, Ohio (United States)

    2010-07-01

    Ruthenium sulfoxides exhibit light-induced linkage isomerization of the SO-bond with remarkable photosensitivity S=(0.25{+-}0.03) Ws cm{sup -1} and extended lifetimes of the related metastable states in the order of 10{sup 4} s. The isomerization is accompanied with tremendous changes of the optical extinction up to 9350 cm{sup -1} mol{sup -1} thus enabling the study of linkage isomerization by means of time-resolved optical spectroscopy. Here, the influence of ligand substitution is studied via inspection of the photosensitivity and the generation and relaxation dynamics of the photochromic response as a function of temperature (pump at {lambda}=405 nm, probe at {lambda}=532 nm). The spectra of the modified compounds, where ligands R=Bn, BnCl, and BnMe were attached to OSO, were compared with the reference system [Ru(bpy){sub 2}(OSO)]{sup +}. It turns out, that the new ligands affect the absorption features and the photosensitivity of the system only slightly. In contrast, a strong influence of the thermal relaxation of the metastable states is uncovered. Remarkably, the influence on the frequency factors is much more pronounced than on the activation energies achieved by Arrhenius' law.

  7. The introduction of hydrogen bond and hydrophobicity effects into the rotational isomeric states model for conformational analysis of unfolded peptides

    International Nuclear Information System (INIS)

    Engin, Ozge; Sayar, Mehmet; Erman, Burak

    2009-01-01

    Relative contributions of local and non-local interactions to the unfolded conformations of peptides are examined by using the rotational isomeric states model which is a Markov model based on pairwise interactions of torsion angles. The isomeric states of a residue are well described by the Ramachandran map of backbone torsion angles. The statistical weight matrices for the states are determined by molecular dynamics simulations applied to monopeptides and dipeptides. Conformational properties of tripeptides formed from combinations of alanine, valine, tyrosine and tryptophan are investigated based on the Markov model. Comparison with molecular dynamics simulation results on these tripeptides identifies the sequence-distant long-range interactions that are missing in the Markov model. These are essentially the hydrogen bond and hydrophobic interactions that are obtained between the first and the third residue of a tripeptide. A systematic correction is proposed for incorporating these long-range interactions into the rotational isomeric states model. Preliminary results suggest that the Markov assumption can be improved significantly by renormalizing the statistical weight matrices to include the effects of the long-range correlations

  8. Specific racemization and isomerization of the aspartyl residue of αA-crystallin due to UV-B irradiation

    International Nuclear Information System (INIS)

    Fujii, Noriko; Momose, Yuko; Ishibasi, Yoshihiro; Uemura, Toshimasa; Takita, Masatoshi; Takehana, Makoto

    1997-01-01

    We have reported that the aspartyl (Asp)-151 residue in αA-crystallin in human eye lens was inverted to the D-isomer and isomerized to β-Asp residue with age. We report here that ultraviolet (UV)-B irradiation induces the racemization and isomerization of the Asp-151 residue of αA-crystallin from lenses of 6-week-old rats to form D-isomer and β-Asp residue. Simultaneous racemization and isomerization of the specific Asp residue indicate that the reaction proceeds via formation of a succinimide intermediate. This modification was not observed in UV-A irradiated and normal lenses. UV-B irradiation induced the racemization of only the Asp-151 residue and did not affect the other Asp residues in αA-crystallin. On the other hand, the high molecular weight fraction of the lens protein increased upon UV-B irradiation. Modification of the Asp residue would affect the three-dimensional packing array of the lens protein. (author)

  9. Isomeric ratios in photonuclear reactions of molybdenum isotopes induced by bremsstrahlung in the giant dipole resonance region

    International Nuclear Information System (INIS)

    Tran Duc Thiep; Truong Thi An; Phan Viet Cuong; Nguyen The Vinh; Bui Minh Hue; Belov, A.G.; Maslov, O.D.; Mishinsky, G.V.; Zhemenik, V.I.

    2017-01-01

    We have determined the isomeric ratios of isomeric pairs "9"7"m","gNb, "9"5"m","gNb and "9"1"m","gMo produced in "9"8Mo(γ, p)"9"7"m","gNb, "9"6Mo(γ, p)"9"5"m","gNb and "9"2Mo(γ, n)"9"1"m","gMo photonuclear reactions in the giant dipole resonance (GDR) region by the activation method. The results were analyzed, discussed and compared with the similar data from literature to examine the role of excitation energy, neutron configuration, channel effect, and direct and pre-equilibrium processes in (γ, p) photonuclear reactions. In this work the isomeric ratios for "9"7"m","gNb from 14 to 19 MeV, for "1"9"5"m","gNb from 14 to 24 MeV except 20 and 23.5 MeV and for "9"1"m","gMo at 14 and 15 MeV were first measured.

  10. The thermal Z-isomerization-induced change in solubility and physical properties of (all-E)-lycopene.

    Science.gov (United States)

    Murakami, Kazuya; Honda, Masaki; Takemura, Ryota; Fukaya, Tetsuya; Kubota, Mitsuhiro; Wahyudiono; Kanda, Hideki; Goto, Motonobu

    2017-09-16

    The effect of Z-isomerization of (all-E)-lycopene on its solubility in organic solvents and physical properties was investigated. Lycopene samples containing different Z-isomer contents (23.8%, 46.9%, and 75.6% of total lycopene) were prepared from high-purity (all-E)-lycopene by thermal Z-isomerization in dichloromethane (CH 2 Cl 2 ). As the Z-isomer content increased, the relative solubility of lycopene significantly improved. Although (all-E)-lycopene barely dissolved in ethanol (0.6 mg/L), the solubilities of lycopene containing 23.8%, 46.9%, and 75.6% Z-isomers were 484.5, 914.7, and 2401.7 mg/L, respectively. Furthermore, differential scanning calorimetry (DSC), powder X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses clearly indicated that (all-E)-lycopene was present in the crystal state, while Z-isomers of lycopene were present in amorphous states. A number of studies have suggested that Z-isomers of lycopene are better absorbed in the human body than the all-E-isomer. This may be due to the change in solubility and physical properties of lycopene by the Z-isomerization. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. First spatial separation of a heavy ion isomeric beam with a multiple-reflection time-of-flight mass spectrometer

    Science.gov (United States)

    Dickel, T.; Plaß, W. R.; Ayet San Andres, S.; Ebert, J.; Geissel, H.; Haettner, E.; Hornung, C.; Miskun, I.; Pietri, S.; Purushothaman, S.; Reiter, M. P.; Rink, A.-K.; Scheidenberger, C.; Weick, H.; Dendooven, P.; Diwisch, M.; Greiner, F.; Heiße, F.; Knöbel, R.; Lippert, W.; Moore, I. D.; Pohjalainen, I.; Prochazka, A.; Ranjan, M.; Takechi, M.; Winfield, J. S.; Xu, X.

    2015-05-01

    211Po ions in the ground and isomeric states were produced via 238U projectile fragmentation at 1000 MeV/u. The 211Po ions were spatially separated in flight from the primary beam and other reaction products by the fragment separator FRS. The ions were energy-bunched, slowed-down and thermalized in a gas-filled cryogenic stopping cell (CSC). They were then extracted from the CSC and injected into a high-resolution multiple-reflection time-of-flight mass spectrometer (MR-TOF-MS). The excitation energy of the isomer and, for the first time, the isomeric-to-ground state ratio were determined from the measured mass spectrum. In the subsequent experimental step, the isomers were spatially separated from the ions in the ground state by an ion deflector and finally collected with a silicon detector for decay spectroscopy. This pioneering experimental result opens up unique perspectives for isomer-resolved studies. With this versatile experimental method new isomers with half-lives longer than a few milliseconds can be discovered and their decay properties can be measured with highest sensitivity and selectivity. These experiments can be extended to studies with isomeric beams in nuclear reactions.

  12. Advances in gamma ray resonant scattering and absorption long-lived isomeric nuclear states

    CERN Document Server

    Davydov, Andrey V

    2015-01-01

    This book presents the basics and advanced topics of research of gamma ray physics. It describes measuring of  Fermi surfaces with gamma resonance spectroscopy and the theory of angular distributions of resonantly scattered gamma rays. The dependence of excited-nuclei average lifetime on the shape of the exciting-radiation spectrum and electron binding energies in the spectra of scattered gamma rays is described. Resonant excitation by gamma rays of nuclear isomeric states with long lifetime leads to the emission and absorption lines. In the book, a new gamma spectroscopic method, gravitational gamma spectrometry, is developed. It has a resolution hundred million times higher than the usual Mössbauer spectrometer. Another important topic of this book is resonant scattering of annihilation quanta by nuclei with excited states in connection with positron annihilation. The application of the methods described is to explain the phenomenon of Coulomb fragmentation of gamma-source molecules and resonant scatt...

  13. Membrane Materials and Technology for Xylene Isomers Separation and Isomerization via Pervaporation

    KAUST Repository

    Bilaus, Rakan

    2014-11-01

    P-xylene is one of the highly influential commodities in the petrochemical industry. It is used to make 90% of the world’s third largest plastic production, polyethylene terephthalate (PET). With a continuously increasing demand, the current technology’s high energy intensity has become a growing concern. Membrane separation technology is a potential low-energy alternative. Polymeric membranes were investigated in a pervaporation experiment to separate xylene isomers. Polymers of intrinsic microporosity (PIMs) as well as polyimides (PIM-PI), including thermally cross-linked PIM-1, PIM-6FDA-OH and thermally-rearranged PIM-6FDA-OH were investigated as potential candidates. Although they exhibited extremely high permeability to xylenes, selectivity towards p-xylene was poor. This was attributed to the polymers low chemical resistance which was apparent in their strong tendency to swell in xylenes. Consequently, a perfluoro-polymer, Teflon AF 2400, with a high chemical resistance was tested, which resulted in a slightly improved selectivity. A super acid sulfonated perfluoro-polymer (Nafion-H) was used as reactive membrane for xylenes isomerization. The membrane exhibited high catalytic activity, resulting in 19.5% p-xylene yield at 75ᵒC compared to 20% p-xylene yield at 450ᵒC in commercial fixed bed reactors. Nafion-H membrane outperforms the commercial technology with significant energy savings.

  14. Ensemble of Transition State Structures for the Cis-Trans Isomerization of N-Methylacetamide

    Energy Technology Data Exchange (ETDEWEB)

    Mantz, Yves A. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Branduardi, Davide [Italian Inst. of Technology, Genoa (Italy); Bussi, Giovanni [Univ. of Modena and Reggio Emilia and INFM-CNR (Italy); Parrinello, Michele [ETH Zurich, Lugano (Switzerland). Dept. of Chemistry and Applied Biosciences

    2009-09-17

    The cis-trans isomerization of N-methylacetamide (NMA), a model peptidic fragment, is studied theoretically in vacuo and in explicit water solvent at 300 K using the metadynamics technique. The computed cis-trans free energy difference is very similar for NMA(g) and NMA(aq), in agreement with experimental measurements of population ratios and theoretical studies at 0 K. By exploiting the flexibility in the definition of a pair of recently introduced collective variables (Branduardi, D.; Gervasio, F. L.; Parrinello, M. J. Chem. Phys. 2007, 126, 054103), an ensemble of transition state structures is generated at finite temperature for both NMA(g) and NMA(aq), as verified by computing committor distribution functions. Ensemble members of NMA(g) are shown to have correlated values of the backbone dihedral angle and a second dihedral angle involving the amide hydrogen atom. The dynamical character of these structures is preserved in the presence of solvent, whose influence on the committor functions can be modeled using effective friction/noise terms.

  15. A comparative cytotoxicity study of isomeric alkylphthalates to metabolically variant bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Sandy, Edward H. [Key Laboratory of Biogeology and Environmental Geology Laboratory of Chinese Ministry of Education and School of Environmental Studies and Sino-Hungarian Joint Laboratory of Environmental Science and Health, China University of Geosciences, Wuhan 430074 (China); Chemistry Department, Fourah Bay College, University of Sierra Leone, Freetown (Sierra Leone); Yao Jun, E-mail: yaojun@cug.edu.cn [Key Laboratory of Biogeology and Environmental Geology Laboratory of Chinese Ministry of Education and School of Environmental Studies and Sino-Hungarian Joint Laboratory of Environmental Science and Health, China University of Geosciences, Wuhan 430074 (China); Zheng Shixue [State Key Laboratory of Agricultural Microbiology, College of Life Science and Technology, Huazhong Agricultural University, Wuhan 430070 (China); Gogra, Alhaji B.; Chen Huilun [Key Laboratory of Biogeology and Environmental Geology Laboratory of Chinese Ministry of Education and School of Environmental Studies and Sino-Hungarian Joint Laboratory of Environmental Science and Health, China University of Geosciences, Wuhan 430074 (China); Zheng Hui [State Key Laboratory of Agricultural Microbiology, College of Life Science and Technology, Huazhong Agricultural University, Wuhan 430070 (China); Yormah, Thomas B.R. [Chemistry Department, Fourah Bay College, University of Sierra Leone, Freetown (Sierra Leone); Zhang Xin [Yale School of Forestry and Environmental Studies, Yale University, 195 Prospect St., New Haven, CT 06511 (United States); Zaray, Gyula [Department of Chemical Technology and Environmental Chemistry, Eoetvoes University, H-1518 Budapest, P.O. Box 32 (Hungary); Ceccanti, Brunello [Institute of Ecosystem Studies (ISE)-Italian National Research Council (ICT-CNR) (Italy); Choi, Martin M.F., E-mail: mfchoi@hkbu.edu.hk [Department of Chemistry, Hong Kong Baptist University, 224 Waterloo Road, Kowloon Tong (Hong Kong)

    2010-10-15

    This work investigated the toxicity of two isomeric alkylphthalates, i.e., di-n-octyl phthalate (DOP) and di-2-ethylhexyl phthalate (DEHP) to two model bacteria, Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis), which have been previously used to study the toxicity of environmental pollutants. Microcalorimetry was used as the key analytical tool alongside scanning electron microscopy (SEM) and traditional microbiology techniques. The thermokinetic parameters from microcalorimetry showed that the phthalates had a biphasic effect on the metabolic activities of the bacteria; serving as energy sources for the bacteria thereby stimulating their growth at low dosages ({<=}150 {mu}g/mL), but displaying inhibitory effects at higher dosages ({>=}300 {mu}g/mL), indicated by a sharp decrease in growth rate constants at 450 {mu}g/mL. The SEM revealed that the bacterial cells were morphological deformed, with shrunk cells and elongated strands at 600 {mu}g/mL of both phthalates. The elongated strands inferred that the phthalates inhibited the reproductive processes of the bacteria by possibly impeding some stages of cell division. The half inhibitory concentrations of the phthalates showed that DEHP was more toxic than DOP. Additionally, E. coli, a facultative anaerobe, was more susceptible to the toxic effects of phthalates than B. subtilis, an obligate aerobe capable of forming endospores crucial for tolerating extreme environmental conditions.

  16. How to compute isomerization energies of organic molecules with quantum chemical methods.

    Science.gov (United States)

    Grimme, Stefan; Steinmetz, Marc; Korth, Martin

    2007-03-16

    The reaction energies for 34 typical organic isomerizations including oxygen and nitrogen heteroatoms are investigated with modern quantum chemical methods that have the perspective of also being applicable to large systems. The experimental reaction enthalpies are corrected for vibrational and thermal effects, and the thus derived "experimental" reaction energies are compared to corresponding theoretical data. A series of standard AO basis sets in combination with second-order perturbation theory (MP2, SCS-MP2), conventional density functionals (e.g., PBE, TPSS, B3-LYP, MPW1K, BMK), and new perturbative functionals (B2-PLYP, mPW2-PLYP) are tested. In three cases, obvious errors of the experimental values could be detected, and accurate coupled-cluster [CCSD(T)] reference values have been used instead. It is found that only triple-zeta quality AO basis sets provide results close enough to the basis set limit and that sets like the popular 6-31G(d) should be avoided in accurate work. Augmentation of small basis sets with diffuse functions has a notable effect in B3-LYP calculations that is attributed to intramolecular basis set superposition error and covers basic deficiencies of the functional. The new methods based on perturbation theory (SCS-MP2, X2-PLYP) are found to be clearly superior to many other approaches; that is, they provide mean absolute deviations of less than 1.2 kcal mol-1 and only a few (computational thermochemistry methods.

  17. Design Efficient and Ultralong Pure Organic Room-Temperature Phosphorescent Materials by Structural Isomerism.

    Science.gov (United States)

    Xiong, Yu; Zhao, Zheng; Zhao, Wei Jun; Ma, Hui Li; Peng, Qian; He, Zi Kai; Zhang, Xue Peng; Chen, Yun Cong; He, Xue Wen; Lam, Jacky; Tang, Ben Zhong

    2018-05-08

    Pure organic materials with ultralong room temperature phosphorescence (RTP) are attractive alternatives to inorganic phosphors. However, without heavy atoms and carbonyl or heteroatomic groups, they generally show inefficient intersystem crossing (ISC) due to the weak spin-orbit coupling (SOC). Many efforts have been made to enhance SOC but examples in realizing both efficient and ultralong RTP have been limited. Here we present a novel design principle based on the realization of small energy gap between the lowest singlet and triplet states (ΔEST) and pure ππ* configuration of the lowest triplet state (T1) via structural isomerism to obtain efficient and ultralong RTP materials. The meta-isomer of carbazole-substituted methyl benzoate exhibits an ultralong lifetime of 795.0 ms with a quantum yield of 2.1%, whose performance is among the best RTP materials reported so far. Study on the structure-property relationship demonstrates that the varied steric and conjugation effects imposed by ester substituent at different positions are responsible for the small ΔEST and pure ππ* configuration of T1. This rational design will open a new avenue for exploring novel pure organic RTP materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. The decay of 399 KeV isomeric state in 197Pt

    International Nuclear Information System (INIS)

    Soares, J.C.; Melo, A.A.; Gil, F.B.; Dias, H.

    1981-02-01

    The nuclear levels in 197 Pt have been studied from decay of 95.4 min 197 (sup m)Pt. The isomeric state was produced by (n,#betta#) reaction on the enriched 196 Pt. The #betta#-ray spectra have been observed with a hyperpure Ge detector and a large volume Ge(Li) detector. The half lives of the 399 KeV and the 53 KeV states were determined with improved precision. The results are: T1/2 (399 KeV) = 95.41 +- 0.18 min and T1/2(53 KeV) = 16.58 +- 0.17 ns. The g-factor of the 53 Kev 5/2 - state has been measured by the gamma-gamma time differential perturbed angular correlation (TDPAC) method in an external magnetic field of 25,1 kG using the 346 - 53 KeV gamma cascade. The value of g-factor was obtained to be + 0.335 +- 0.010. This result is compared with the known g-factors of the similar states in 195 Pt, and in 197 Hg and 199 Hg and also with the theoretical calculations based on the quasiparticle-phonon coupling scheme. Possibility of using the 346 - 53 KeV gamma cascade in 197 Pt in the future TDPAC studies is discussed. (Author) [pt

  19. Identification of levels above 6{sup -} isomeric state in {sup 66}Cu

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Purnima; Palit, R.; Biswas, S.; Saha, S. [Tata Institute of Fundamental Research, Department of Nuclear and Atomic Physics, Mumbai (India); Choudhury, D. [Horia Hulubei National Institute for Physics and Nuclear Engineering, ELI-NP, Magurele (Romania); Srivastava, P.C. [Indian Institute of Technology Roorkee, Department of Physics, Roorkee (India); Sethi, J. [Tata Institute of Fundamental Research, Department of Nuclear and Atomic Physics, Mumbai (India); University of Maryland, Department of Chemistry and Biochemistry, College Park, MD (United States)

    2017-04-15

    Excited states in odd-odd {sup 66}Cu were investigated in a reaction between a 136 MeV {sup 30}Si beam and a {sup 65}Cu target with the Indian National Gamma Array. Six new transitions have been identified including four transitions feeding the 600 ns 6{sup -} isomeric state from an investigation of prompt-prompt and prompt-delayed coincidence events. The results of the present work have extended the level structure of this nucleus up to I{sup π} = (9{sup -}). In addition, new information on the set of πp{sub 3/2}νg{sub 9/2} multiplets in this nucleus have been added. Shell model calculations were performed within the fpg{sub 9/2} and f{sub 5/2}pg{sub 9/2} model spaces. The results of shell model calculations using the fpg{sub 9/2} model space have been observed to be in better agreement with experimental excitation energies up to the highest spin observed. The results of the present work highlight the necessity of f{sub 7/2} proton holes to describe the positive as well as negative parity states in {sup 66}Cu. (orig.)

  20. High rate gamma spectroscopy system for activation analysis of short-lived isomeric transitions

    Energy Technology Data Exchange (ETDEWEB)

    Westphall, G P [Atominstitut der Oesterreichischen Hochschulen, Vienna

    1976-07-15

    A high rate spectroscopy system specially suited for measurement of short-lived isomeric transitions is described, which, as part of a fast activation analysis facility at the TRIGA Mark II reactor, provides for automatic recording and immediate evaluation of gamma spectra taken from nuclides activated at stationary or pulsed reactor power. The system consists of a commercial de-coupled Ge(Li)-detector of 70 cm/sup 3/ modified for recycling operation for input rates in excess of 500000 c/s /sup 60/Co, a time variant trapezoidal shaping section and a fast constant dead-time ADC coupled to a programmed multichannel analyzer. Novel circuits for efficient pile-up rejection and time variant base line restoration extend the concept of gated integration up to count rates of more than 200000 c/s /sup 60/Co. Time-sequenced recording of spectra is performed by a minicomputer operated as a front-end processor of a larger laboratory computer, where final data processing takes place. New concepts for very simple and cost-effective implementation of multichannel analyzers by means of general purpose small computers are described.