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.

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

Equilibria and Free Vibration of a Two-Pulley Belt-Driven System with Belt Bending Stiffness

Directory of Open Access Journals (Sweden)

Jieyu Ding

2014-01-01

Full Text Available Nonlinear equilibrium curvatures and free vibration characteristics of a two-pulley belt-driven system with belt bending stiffness and a one-way clutch are investigated. With nonlinear dynamical tension, the transverse vibrations of the translating belt spans and the rotation motions of the pulleys and the accessory shaft are coupled. Therefore, nonlinear piecewise discrete-continuous governing equations are established. Considering the bending stiffness of the translating belt spans, the belt spans are modeled as axially moving beams. The pattern of equilibria is a nontrivial solution. Furthermore, the nontrivial equilibriums of the dynamical system are numerically determined by using two different approaches. The governing equations of the vibration near the equilibrium solutions are derived by introducing a coordinate transform. The natural frequencies of the dynamical systems are studied by using the Galerkin method with various truncations and the differential and integral quadrature methods. Moreover, the convergence of the Galerkin truncation is investigated. Numerical results reveal that the study needs 16 terms after truncation in order to determine the free vibration characteristics of the pulley-belt system with the belt bending stiffness. Furthermore, the first five natural frequencies are very sensitive to the bending stiffness of the translating belt.

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

Microwave discharge electrodeless lamps (MDEL). Part VII. Photo-isomerization of trans-urocanic acid in aqueous media driven by UV light from a novel Hg-free Dewar-like microwave discharge thermally-insulated electrodeless lamp (MDTIEL). Performance evaluation.

Science.gov (United States)

Horikoshi, Satoshi; Sato, Tatsuro; Sakamoto, Kazutami; Abe, Masahiko; Serpone, Nick

2011-07-01

A novel mercury-free Dewar-like (double-walled structure) microwave discharge thermally-insulated electrodeless lamp (MDTIEL) was fabricated and its performance evaluated using the photo-isomerization of trans-urocanic acid (trans-UA) in aqueous media as a test process driven by the emitted UV light when ignited with microwave radiation. The photo-isomerization processes trans-UA → cis-UA and cis-UA → trans-UA were re-visited using light emitted from a conventional high-pressure Hg light source and examined for the influence of UV light irradiance and solution temperature; the temperature dependence of the trans → cis process displayed a negative activation energy, E(a) = -1.3 cal mol(-1). To control the photo-isomerization of urocanic acid from the heat usually dissipated by a microwave discharge electrodeless lamp (single-walled MDEL), it was necessary to suppress the microwave-initiated heat. For comparison, the gas-fill in the MDEL lamp, which typically consists of a mixture of Hg and Ar, was changed to the more eco-friendly N(2) gas in the novel MDTIEL device. The dynamics of the photo-isomerization of urocanic acid driven by the UV wavelengths of the N(2)-MDTIEL light source were compared to those from the more conventional single-walled N(2)-MDEL and Hg/Ar-MDEL light sources, and with those from the Hg lamp used to irradiate, via a fiber optic, the photoreactor located in the wave-guide of the microwave apparatus. The heating efficiency of a solution with the double-walled N(2)-MDTIEL was compared to the efficiency from the single-walled N(2)-MDEL device. Advantages of N(2)-MDTIEL are described from a comparison of the dynamics of the trans-UA → cis-UA process on the basis of unit surface area of the lamp and unit power consumption. The considerably lower temperature on the external surface of the N(2)-MDTIEL light source should make it attractive in carrying out photochemical reactions that may be heat-sensitive such as the photothermochromic

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.

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.

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.

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.

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

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.

Imperfections of the North-Atlantic wind-driven ocean circulation: continental geometry and windstress shape

NARCIS (Netherlands)

Dijkstra, H.A.; Molemaker, M.J.

1998-01-01

Multiple equilibria of the wind-driven gyres have been found in idealized quasi- geostrophic and shallow water models.In this paper we demonstrate that multiple equilibria persist within a reduced gravity shallow water model under quite realis- tic continental geometry and windstress orcing for

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.%.

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

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

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

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

Electric field driven plasmon dispersion in AlGaN/GaN high electron mobility transistors

International Nuclear Information System (INIS)

Tan Ren-Bing; Qin Hua; Zhang Xiao-Yu; Xu Wen

2013-01-01

We present a theoretical study on the electric field driven plasmon dispersion of the two-dimensional electron gas (2DEG) in AlGaN/GaN high electron mobility transistors (HEMTs). By introducing a drifted Fermi—Dirac distribution, we calculate the transport properties of the 2DEG in the AlGaN/GaN interface by employing the balance-equation approach based on the Boltzmann equation. Then, the nonequilibrium Fermi—Dirac function is obtained by applying the calculated electron drift velocity and electron temperature. Under random phase approximation (RPA), the electric field driven plasmon dispersion is investigated. The calculated results indicate that the plasmon frequency is dominated by both the electric field E and the angle between wavevector q and electric field E. Importantly, the plasmon frequency could be tuned by the applied source—drain bias voltage besides the gate voltage (change of the electron density)

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)

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.

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

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.

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.

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.)

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.

Synthesis of zeolite-zeolite (mfi-fau) composite catalysts for the isomerization of n-hexane

International Nuclear Information System (INIS)

Ghouri, A.S; Usman, M.R.

2017-01-01

In this research work, the aim is to produce a relatively novel zeolite-zeolite (MFI-FAU) composite catalyst having better potential of catalyzing isomerization of lighter hydrocarbons such as light naphtha, n-pentane, n-hexane, n-heptane and mixture thereof. A series of zeolite-zeolite (MFI-FAU) composite catalysts have been synthesized by incorporating previous practices and techniques. The catalytic performance of as-synthesized zeolite-zeolite (MFI-FAU) composite catalysts have been investigated by isomerizing 95% pure n-hexane in conventional fixed bed flow micro-reactor at temperature 200-240 ºC under atmospheric pressure. In order to explore chemical and physical features of zeolite-zeolite (MFI-FAU) composite catalysts, they are examined and characterized using powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectrometry (EDX), N2 adsorption-desorption measurements (BET, BJH, t-plot measurements) and Fourier transform infrared (FTIR) spectroscopy equipped with attenuated total reflectance (ATR) arrangements. (author)

Theoretical model based on the memory effect for the strange photoisomerization kinetics of diarylethene derivatives dispersed on polymer films

International Nuclear Information System (INIS)

Seki, Kazuhiko; Tachiya, M.

2007-01-01

In the present paper the authors present a theoretical model to explain the kinetics involving the induction period observed by Irie et al. [Nature (London) 420, 759 (2002)] for photoisomerization of diarylethene derivatives dispersed on polymer films at a single molecular level. In the model we assume that both ground state and excited state free energy landscapes which result from the interaction between the photochromic molecule and the surrounding polymer are rugged and have several local minima along the pathway to the critical point at which isomerization actually occurs. We assume that after one photoexcitation a fraction of the photochromic molecule moves to a new local minimum and stays there, although the other fraction returns to the original local minimum. The former effect is referred to as the memory effect. After repeated photoexcitations the photochromic molecule moves gradually from one local minimum to another in the pathway to the isomerization point. It finally reaches the isomerization point, where isomerization occurs. Their model successfully reproduces the kinetics of photoisomerization of diarylethene derivatives dispersed on polymer films observed experimentally

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)

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)

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

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.

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.

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.

Stability of nonlinear Vlasov-Poisson equilibria through spectral deformation and Fourier-Hermite expansion.

Science.gov (United States)

Siminos, Evangelos; Bénisti, Didier; Gremillet, Laurent

2011-05-01

We study the stability of spatially periodic, nonlinear Vlasov-Poisson equilibria as an eigenproblem in a Fourier-Hermite basis (in the space and velocity variables, respectively) of finite dimension, N. When the advection term in the Vlasov equation is dominant, the convergence with N of the eigenvalues is rather slow, limiting the applicability of the method. We use the method of spectral deformation introduced by Crawford and Hislop [Ann. Phys. (NY) 189, 265 (1989)] to selectively damp the continuum of neutral modes associated with the advection term, thus accelerating convergence. We validate and benchmark the performance of our method by reproducing the kinetic dispersion relation results for linear (spatially homogeneous) equilibria. Finally, we study the stability of a periodic Bernstein-Greene-Kruskal mode with multiple phase-space vortices, compare our results with numerical simulations of the Vlasov-Poisson system, and show that the initial unstable equilibrium may evolve to different asymptotic states depending on the way it was perturbed. © 2011 American Physical Society

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.

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)

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.

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

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

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.

Ir-Driven Dynamics of the 3-AMINOPHENOL-AMMONIA Complex

Science.gov (United States)

Heid, Cornelia G.; Merrill, W. G.; Case, Amanda; Crim, Fleming

2014-06-01

We report on gas-phase experiments investigating the predissociation and possible IR-driven isomerization of the 3-aminophenol-ammonia complex (3-AP-NH3). A molecular beam of 3-AP-NH3 is vibrationally excited with pulsed IR light, initiating an intramolecular vibrational redistribution and subsequent dissociation. The 3-AP fragment is then probed state-selectively via multiphoton ionization (REMPI) and time-of-flight mass spectrometry. Of particular interest is an IR-driven feature which we associate tentatively with a trans-cis isomerization process. We see clear correlation between the excitation of specific vibrational modes (namely the NH3 symmetric and OH stretches) and the presence of this feature, as evidenced by IR-action and IR-depletion spectra. The feature persists atop a broader signal which we assign to the predissociation of the complex and whose cutoff in REMPI-action experiments provides an upper bound on the dissociation energy for 3-AP-NH3.

Modeling of LH current drive in self-consistent elongated tokamak MHD equilibria

International Nuclear Information System (INIS)

Blackfield, D.T.; Devoto, R.S.; Fenstermacher, M.E.; Bonoli, P.T.; Porkolab, M.; Yugo, J.

1989-01-01

Calculations of non-inductive current drive typically have been used with model MHD equilibria which are independently generated from an assumed toroidal current profile or from a fit to an experiment. Such a method can lead to serious errors since the driven current can dramatically alter the equilibrium and changes in the equilibrium B-fields can dramatically alter the current drive. The latter effect is quite pronounced in LH current drive where the ray trajectories are sensitive to the local values of the magnetic shear and the density gradient. In order to overcome these problems, we have modified a LH simulation code to accommodate elongated plasmas with numerically generated equilibria. The new LH module has been added to the ACCOME code which solves for current drive by neutral beams, electric fields, and bootstrap effects in a self-consistent 2-D equilibrium. We briefly describe the model in the next section and then present results of a study of LH current drive in ITER. 2 refs., 6 figs., 2 tabs

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.

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.

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

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)....

{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.

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...

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...

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.

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.

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

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.

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.

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.)

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

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.

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].

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

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.

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

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.

Controllable Absorption and Dispersion Properties of an RF-driven Five-Level Atom in a Double-Band Photonic-Band-Gap Material

International Nuclear Information System (INIS)

Ding Chunling; Li Jiahua; Yang Xiaoxue

2011-01-01

The probe absorption-dispersion spectra of a radio-frequency (RF)-driven five-level atom embedded in a photonic crystal are investigated by considering the isotropic double-band photonic-band-gap (PBG) reservoir. In the model used, the two transitions are, respectively, coupled by the upper and lower bands in such a PBG material, thus leading to some curious phenomena. Numerical simulations are performed for the optical spectra. It is found that when one transition frequency is inside the band gap and the other is outside the gap, there emerge three peaks in the absorption spectra. However, for the case that two transition frequencies lie inside or outside the band gap, the spectra display four absorption profiles. Especially, there appear two sharp peaks in the spectra when both transition frequencies exist inside the band gap. The influences of the intensity and frequency of the RF-driven field on the absorptive and dispersive response are analyzed under different band-edge positions. It is found that a transparency window appears in the absorption spectra and is accompanied by a very steep variation of the dispersion profile by adjusting system parameters. These results show that the absorption-dispersion properties of the system depend strongly on the RF-induced quantum interference and the density of states (DOS) of the PBG reservoir. (electromagnetism, optics, acoustics, heat transfer, classical mechanics, and fluid dynamics)

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

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

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.

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)

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)

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

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...

Ultrafast Dynamics in Light-Driven Molecular Rotary Motors Probed by Femtosecond Stimulated Raman Spectroscopy

NARCIS (Netherlands)

Hall, Christopher R.; Conyard, Jamie; Heisler, Ismael A.; Jones, Garth; Frost, James; Browne, Wesley R.; Feringa, Ben L.; Meech, Stephen R.

2017-01-01

Photochemical isomerization in sterically crowded chiral alkenes is the driving force for molecular rotary motors in nanoscale machines. Here the excited-state dynamics and structural evolution of the prototypical light-driven rotary motor are followed on the ultrafast time scale by femtosecond

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

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...

Large eddy simulation of fire-induced buoyancy driven plume dispersion in an urban street canyon under perpendicular wind flow

Energy Technology Data Exchange (ETDEWEB)

Hu, L.H., E-mail: hlh@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China); Huo, R.; Yang, D. [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China)

2009-07-15

The dispersion of fire-induced buoyancy driven plume in and above an idealized street canyon of 18 m (width) x 18 m (height) x 40 m (length) with a wind flow perpendicular to its axis was investigated by Fire Dynamics Simulator (FDS), Large Eddy Simulation (LES). Former studies, such as that by Oka [T.R. Oke, Street design and urban canopy layer climate, Energy Build. 11 (1988) 103-113], Gayev and Savory [Y.A. Gayev, E. Savory, Influence of street obstructions on flow processes within street canyons. J. Wind Eng. Ind. Aerodyn. 82 (1999) 89-103], Xie et al. [S. Xie, Y. Zhang, L. Qi, X. Tang, Spatial distribution of traffic-related pollutant concentrations in street canyons. Atmos. Environ. 37 (2003) 3213-3224], Baker et al. [J. Baker, H. L. Walker, X. M. Cai, A study of the dispersion and transport of reactive pollutants in and above street canyons-a large eddy simulation, Atmos. Environ. 38 (2004) 6883-6892] and Baik et al. [J.-J. Baik, Y.-S. Kang, J.-J. Kim, Modeling reactive pollutant dispersion in an urban street canyon, Atmos. Environ. 41 (2007) 934-949], focus on the flow pattern and pollutant dispersion in the street canyon with no buoyancy effect. Results showed that with the increase of the wind flow velocity, the dispersion pattern of a buoyant plume fell into four regimes. When the wind flow velocity increased up to a certain critical level, the buoyancy driven upward rising plume was re-entrained back into the street canyon. This is a dangerous situation as the harmful fire smoke will accumulate to pollute the environment and thus threaten the safety of the people in the street canyon. This critical re-entrainment wind velocity, as an important parameter to be concerned, was further revealed to increase asymptotically with the heat/buoyancy release rate of the fire.

Large eddy simulation of fire-induced buoyancy driven plume dispersion in an urban street canyon under perpendicular wind flow.

Science.gov (United States)

Hu, L H; Huo, R; Yang, D

2009-07-15

The dispersion of fire-induced buoyancy driven plume in and above an idealized street canyon of 18 m (width) x 18 m (height) x 40 m (length) with a wind flow perpendicular to its axis was investigated by Fire Dynamics Simulator (FDS), Large Eddy Simulation (LES). Former studies, such as that by Oka [T.R. Oke, Street design and urban canopy layer climate, Energy Build. 11 (1988) 103-113], Gayev and Savory [Y.A. Gayev, E. Savory, Influence of street obstructions on flow processes within street canyons. J. Wind Eng. Ind. Aerodyn. 82 (1999) 89-103], Xie et al. [S. Xie, Y. Zhang, L. Qi, X. Tang, Spatial distribution of traffic-related pollutant concentrations in street canyons. Atmos. Environ. 37 (2003) 3213-3224], Baker et al. [J. Baker, H. L. Walker, X. M. Cai, A study of the dispersion and transport of reactive pollutants in and above street canyons--a large eddy simulation, Atmos. Environ. 38 (2004) 6883-6892] and Baik et al. [J.-J. Baik, Y.-S. Kang, J.-J. Kim, Modeling reactive pollutant dispersion in an urban street canyon, Atmos. Environ. 41 (2007) 934-949], focus on the flow pattern and pollutant dispersion in the street canyon with no buoyancy effect. Results showed that with the increase of the wind flow velocity, the dispersion pattern of a buoyant plume fell into four regimes. When the wind flow velocity increased up to a certain critical level, the buoyancy driven upward rising plume was re-entrained back into the street canyon. This is a dangerous situation as the harmful fire smoke will accumulate to pollute the environment and thus threaten the safety of the people in the street canyon. This critical re-entrainment wind velocity, as an important parameter to be concerned, was further revealed to increase asymptotically with the heat/buoyancy release rate of the fire.

Large eddy simulation of fire-induced buoyancy driven plume dispersion in an urban street canyon under perpendicular wind flow

International Nuclear Information System (INIS)

Hu, L.H.; Huo, R.; Yang, D.

2009-01-01

The dispersion of fire-induced buoyancy driven plume in and above an idealized street canyon of 18 m (width) x 18 m (height) x 40 m (length) with a wind flow perpendicular to its axis was investigated by Fire Dynamics Simulator (FDS), Large Eddy Simulation (LES). Former studies, such as that by Oka [T.R. Oke, Street design and urban canopy layer climate, Energy Build. 11 (1988) 103-113], Gayev and Savory [Y.A. Gayev, E. Savory, Influence of street obstructions on flow processes within street canyons. J. Wind Eng. Ind. Aerodyn. 82 (1999) 89-103], Xie et al. [S. Xie, Y. Zhang, L. Qi, X. Tang, Spatial distribution of traffic-related pollutant concentrations in street canyons. Atmos. Environ. 37 (2003) 3213-3224], Baker et al. [J. Baker, H. L. Walker, X. M. Cai, A study of the dispersion and transport of reactive pollutants in and above street canyons-a large eddy simulation, Atmos. Environ. 38 (2004) 6883-6892] and Baik et al. [J.-J. Baik, Y.-S. Kang, J.-J. Kim, Modeling reactive pollutant dispersion in an urban street canyon, Atmos. Environ. 41 (2007) 934-949], focus on the flow pattern and pollutant dispersion in the street canyon with no buoyancy effect. Results showed that with the increase of the wind flow velocity, the dispersion pattern of a buoyant plume fell into four regimes. When the wind flow velocity increased up to a certain critical level, the buoyancy driven upward rising plume was re-entrained back into the street canyon. This is a dangerous situation as the harmful fire smoke will accumulate to pollute the environment and thus threaten the safety of the people in the street canyon. This critical re-entrainment wind velocity, as an important parameter to be concerned, was further revealed to increase asymptotically with the heat/buoyancy release rate of the fire.

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.

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.

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.

Hydrodynamic dispersion in a combined magnetohydrodynamic- electroosmotic-driven flow through a microchannel with slowly varying wall zeta potentials

Science.gov (United States)

Vargas, C.; Arcos, J.; Bautista, O.; Méndez, F.

2017-09-01

The effective dispersion coefficient of a neutral solute in the combined electroosmotic (EO) and magnetohydrodynamic (MHD)-driven flow of a Newtonian fluid through a parallel flat plate microchannel is studied. The walls of the microchannel are assumed to have modulated and low zeta potentials that vary slowly in the axial direction in a sinusoidal manner. The flow field required to obtain the dispersion coefficient is solved using the lubrication approximation theory. The solution of the electrical potential is based on the Debye-Hückel approximation for a symmetric (Z :Z ) electrolyte solution. The EO and MHD effects, together with the variations in the zeta potentials of the walls, are observed to notably modify the axial distribution of the effective dispersion coefficient. The problem is formulated for two cases of the zeta potential function. Note that the dispersion coefficient primarily depends on the Hartmann number, on the ratio of the half height of the microchannel to the Debye length, and on the assumed variation in the zeta potentials of the walls.

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...

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)

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

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

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.

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.

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

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)

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.

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.

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.

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.

Reaction pathways of photoexcited retinal in proteorhodopsin studied by pump-dump-probe spectroscopy.

Science.gov (United States)

Rupenyan, Alisa; van Stokkum, Ivo H M; Arents, Jos C; van Grondelle, Rienk; Hellingwerf, Klaas J; Groot, Marie Louise

2009-12-17

Proteorhodopsin (pR) is a membrane-embedded proton pump from the microbial rhodopsin family. Light absorption by its retinal chromophore initiates a photocycle, driven by trans/cis isomerization on the femtosecond to picosecond time scales. Here, we report a study on the photoisomerization dynamics of the retinal chromophore of pR, using dispersed ultrafast pump-dump-probe spectroscopy. The application of a pump pulse initiates the photocycle, and with an appropriately tuned dump pulse applied at a time delay after the dump, the molecules in the initial stages of the photochemical process can be de-excited and driven back to the ground state. In this way, we were able to resolve an intermediate on the electronic ground state that represents chromophores that are unsuccessful in isomerization. In particular, the fractions of molecules that undergo slow isomerization (20 ps) have a high probability to enter this state rather than the isomerized K-state. On the ground state reaction surface, return to the stable ground state conformation via a structural or vibrational relaxation occurs in 2-3 ps. Inclusion of this intermediate in the kinetic scheme led to more consistent spectra of the retinal-excited state, and to a more accurate estimation of the quantum yield of isomerization (Phi = 0.4 at pH 6).

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

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...

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

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)

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....

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...

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

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.

Phase equilibria and thermodynamic modeling of ethane and propane hydrates in porous silica gels.

Science.gov (United States)

Seo, Yongwon; Lee, Seungmin; Cha, Inuk; Lee, Ju Dong; Lee, Huen

2009-04-23

In the present study, we examined the active role of porous silica gels when used as natural gas storage and transportation media. We adopted the dispersed water in silica gel pores to substantially enhance active surface for contacting and encaging gas molecules. We measured the three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria of C(2)H(6) and C(3)H(8) hydrates in 6.0, 15.0, 30.0, and 100.0 nm silica gel pores to investigate the effect of geometrical constraints on gas hydrate phase equilibria. At specified temperatures, the hydrate stability region is shifted to a higher pressure region depending on pore size when compared with those of bulk hydrates. Through application of the Gibbs-Thomson relationship to the experimental data, we determined the values for the C(2)H(6) hydrate-water and C(3)H(8) hydrate-water interfacial tensions to be 39 +/- 2 and 45 +/- 1 mJ/m(2), respectively. By using these values, the calculation values were in good agreement with the experimental ones. The overall results given in this study could also be quite useful in various fields, such as exploitation of natural gas hydrate in marine sediments and sequestration of carbon dioxide into the deep ocean.

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...

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)

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.

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...

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)

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%.

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%

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...

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

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...

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....

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...

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].

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

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)

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...

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

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

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.

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.

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

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

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...

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

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

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.

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.

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

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.

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.

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)

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.

Fluctuation-Driven Neural Dynamics Reproduce Drosophila Locomotor Patterns.

Directory of Open Access Journals (Sweden)

Andrea Maesani

2015-11-01

Full Text Available The neural mechanisms determining the timing of even simple actions, such as when to walk or rest, are largely mysterious. One intriguing, but untested, hypothesis posits a role for ongoing activity fluctuations in neurons of central action selection circuits that drive animal behavior from moment to moment. To examine how fluctuating activity can contribute to action timing, we paired high-resolution measurements of freely walking Drosophila melanogaster with data-driven neural network modeling and dynamical systems analysis. We generated fluctuation-driven network models whose outputs-locomotor bouts-matched those measured from sensory-deprived Drosophila. From these models, we identified those that could also reproduce a second, unrelated dataset: the complex time-course of odor-evoked walking for genetically diverse Drosophila strains. Dynamical models that best reproduced both Drosophila basal and odor-evoked locomotor patterns exhibited specific characteristics. First, ongoing fluctuations were required. In a stochastic resonance-like manner, these fluctuations allowed neural activity to escape stable equilibria and to exceed a threshold for locomotion. Second, odor-induced shifts of equilibria in these models caused a depression in locomotor frequency following olfactory stimulation. Our models predict that activity fluctuations in action selection circuits cause behavioral output to more closely match sensory drive and may therefore enhance navigation in complex sensory environments. Together these data reveal how simple neural dynamics, when coupled with activity fluctuations, can give rise to complex patterns of animal behavior.

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.

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.)

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.

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.

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

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.

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....

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.

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.

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

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

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.)

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.

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.

Buoyancy-driven chaotic regimes during solute dispersion in pore networks

International Nuclear Information System (INIS)

Tsakiroglou, C.D.; Theodoropoulou, M.A.; Karoutsos, V.

2005-01-01

In an attempt to investigate gravity effects on solute dispersion at the scale of a pore network, single source-solute transport visualization experiments are performed on glass-etched pore networks of varying morphology and degree of pore-scale heterogeneities. The (lighter) low solute concentration aqueous solution flows steadily through the porous medium and the (heavier) high solute concentration solution is injected at a very low and constant flow rate through an inner port. The transient evolution of the solute concentration distribution over various regions of the pore network is determined at different scales by capturing and video-recording snapshots of the dispersion on PC, measuring automatically the spatial variation of the color intensity of the solution, and transforming the color intensities to solute concentrations. Without the action of gravity, the steady-state dispersion regime changes with Peclet (Pe) number, and the longitudinal and transverse dispersivities are estimated by fitting the experimental datasets to approximate analytic solutions of the advection-dispersion equation. Under the action of gravity, multiple of steady-state solute dispersion regimes is developed at each Pe value, and lobe-shaped instabilities of the solute concentration are observed across the pore network, as the downward flow of the denser (higher solute concentration) fluid is counterbalanced by the upward flow of the less dense (lower solute concentration) fluid. The steady-state dispersion regimes may be periodic, quasi-periodic or chaotic depending on the system parameters. The nature of the transient fluctuations of the average solute concentration is analyzed by identifying the periodicity of the fluctuations, determining the autocorrelation function and the statistical moments of the time series, and inspecting the FFT (fast Fourier transform) power spectra. It is found that the mixing zone tends to be stabilized at higher values of the Peclet (Pe) number

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...

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.

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

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.

(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

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.

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)

Strongly coupled dispersed two-phase flows; Ecoulements diphasiques disperses fortement couples

Energy Technology Data Exchange (ETDEWEB)

Zun, I.; Lance, M.; Ekiel-Jezewska, M.L.; Petrosyan, A.; Lecoq, N.; Anthore, R.; Bostel, F.; Feuillebois, F.; Nott, P.; Zenit, R.; Hunt, M.L.; Brennen, C.E.; Campbell, C.S.; Tong, P.; Lei, X.; Ackerson, B.J.; Asmolov, E.S.; Abade, G.; da Cunha, F.R.; Lhuillier, D.; Cartellier, A.; Ruzicka, M.C.; Drahos, J.; Thomas, N.H.; Talini, L.; Leblond, J.; Leshansky, A.M.; Lavrenteva, O.M.; Nir, A.; Teshukov, V.; Risso, F.; Ellinsen, K.; Crispel, S.; Dahlkild, A.; Vynnycky, M.; Davila, J.; Matas, J.P.; Guazelli, L.; Morris, J.; Ooms, G.; Poelma, C.; van Wijngaarden, L.; de Vries, A.; Elghobashi, S.; Huilier, D.; Peirano, E.; Minier, J.P.; Gavrilyuk, S.; Saurel, R.; Kashinsky, O.; Randin, V.; Colin, C.; Larue de Tournemine, A.; Roig, V.; Suzanne, C.; Bounhoure, C.; Brunet, Y.; Tanaka, A.T.; Noma, K.; Tsuji, Y.; Pascal-Ribot, S.; Le Gall, F.; Aliseda, A.; Hainaux, F.; Lasheras, J.; Didwania, A.; Costa, A.; Vallerin, W.; Mudde, R.F.; Van Den Akker, H.E.A.; Jaumouillie, P.; Larrarte, F.; Burgisser, A.; Bergantz, G.; Necker, F.; Hartel, C.; Kleiser, L.; Meiburg, E.; Michallet, H.; Mory, M.; Hutter, M.; Markov, A.A.; Dumoulin, F.X.; Suard, S.; Borghi, R.; Hong, M.; Hopfinger, E.; Laforgia, A.; Lawrence, C.J.; Hewitt, G.F.; Osiptsov, A.N.; Tsirkunov, Yu. M.; Volkov, A.N.

2003-07-01

This document gathers the abstracts of the Euromech 421 colloquium about strongly coupled dispersed two-phase flows. Behaviors specifically due to the two-phase character of the flow have been categorized as: suspensions, particle-induced agitation, microstructure and screening mechanisms; hydrodynamic interactions, dispersion and phase distribution; turbulence modulation by particles, droplets or bubbles in dense systems; collective effects in dispersed two-phase flows, clustering and phase distribution; large-scale instabilities and gravity driven dispersed flows; strongly coupled two-phase flows involving reacting flows or phase change. Topic l: suspensions particle-induced agitation microstructure and screening mechanisms hydrodynamic interactions between two very close spheres; normal stresses in sheared suspensions; a critical look at the rheological experiments of R.A. Bagnold; non-equilibrium particle configuration in sedimentation; unsteady screening of the long-range hydrodynamic interactions of settling particles; computer simulations of hydrodynamic interactions among a large collection of sedimenting poly-disperse particles; velocity fluctuations in a dilute suspension of rigid spheres sedimenting between vertical plates: the role of boundaries; screening and induced-agitation in dilute uniform bubbly flows at small and moderate particle Reynolds numbers: some experimental results. Topic 2: hydrodynamic interactions, dispersion and phase distribution: hydrodynamic interactions in a bubble array; A 'NMR scattering technique' for the determination of the structure in a dispersion of non-brownian settling particles; segregation and clustering during thermo-capillary migration of bubbles; kinetic modelling of bubbly flows; velocity fluctuations in a homogeneous dilute dispersion of high-Reynolds-number rising bubbles; an attempt to simulate screening effects at moderate particle Reynolds numbers using an hybrid formulation; modelling the two

Extent of intramolecular pi stacks in aqueous solution in mixed-ligand copper(II) complexes formed by heteroaromatic amines and the anticancer and antivirally active 9[2-(phosphonomethoxy)ethyl]guanine (PMEG). A comparison with related acyclic nucleotide analogues

Czech Academy of Sciences Publication Activity Database

Blindauer, C. A.; Sigel, A.; Operschall, B. P.; Griesser, R.; Holý, Antonín; Sigel, H.

2016-01-01

Roč. 103, Jan 8 (2016), s. 248-260 ISSN 0277-5387 Institutional support: RVO:61388963 Keywords : anticancer activity * antivirals * aromatic-ring stacking * isomeric equilibria * nucleotide analogues Subject RIV: CC - Organic Chemistry Impact factor: 1.926, year: 2016

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...

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-...

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

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.

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

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.

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

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)

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.

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.

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.

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.

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.

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.

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...

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

Energetics of the formation and reactions of gaseous ions. Annual progress report for the period September, 16, 1981 to September 15, 1982

International Nuclear Information System (INIS)

Meisels, G.G.

1982-09-01

Research is reported in these areas: range and linear ionization rates of low energy electrons; ion fragmentation from noninterconverting states; competition between isomerization and fragmentation of gaseous ions; precise thermodynamic measurements of gas phase ionic equilibria; and instrumental analyses and developments

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)

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

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....

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-.

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

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

Numerical study of two-fluid flowing equilibria of helicity-driven spherical torus plasmas

International Nuclear Information System (INIS)

Kanki, T.; Nagata, M.; Uyama, T.

2004-01-01

Two-fluid flowing equilibrium configurations of a helicity-driven spherical torus (HD-ST) are numerically determined by using the combination of the finite difference and the boundary element methods. It is found from the numerical results that electron fluids near the central conductor are tied to an external toroidal field and ion fluids are not. The magnetic configurations change from the high-q HD-ST (q>1) with paramagnetic toroidal field and low-β (volume average β value, ∼ 2%) through the helicity-driven spheromak and RFP (reverse field pinch) to the ultra low-q HD-ST (0 ∼ 18%) as the external toroidal field at the inner edge regions decreases and reverses the sign. The two-fluid effects are more significant in this equilibrium transition when the ion diamagnetic drift is dominant in the flowing two-fluid. (authors)

Experimental study of the phase equilibria in the Mg–Zn–Ag ternary system at 300 °C

Energy Technology Data Exchange (ETDEWEB)

Wang, Jian, E-mail: jian.wang@polymtl.ca [Center for Research in Computational Thermochemistry (CRCT), Department of Chemical Engineering, École Polytechnique, Montréal, Québec H3C 3A7 (Canada); Zhang, Yi-Nan [Department of Mechanical Engineering, Concordia University, 1455 De Maisonneuve Blvd. West, Montreal, Quebec H3G 1M8 (Canada); Hudon, Pierre; Jung, In-Ho [Department of Mining and Materials Engineering, McGill University, 3610 University Street, Montreal, Quebec H3A 0C5 (Canada); Medraj, Mamoun [Department of Mechanical Engineering, Concordia University, 1455 De Maisonneuve Blvd. West, Montreal, Quebec H3G 1M8 (Canada); Department of Mechanical and Materials Engineering, Masdar Institute, Masdar City, P.O. Box 54224, Abu Dhabi (United Arab Emirates); Chartrand, Patrice [Center for Research in Computational Thermochemistry (CRCT), Department of Chemical Engineering, École Polytechnique, Montréal, Québec H3C 3A7 (Canada)

2015-08-05

Highlights: • The phase equilibria of Mg–Zn–Ag system at 300 °C were determined. • A bcc continuous ternary solid solution forms between MgAg (bcc-B2) and AgZn (bcc-A2) was determined. • The extended solid solubilities of the sub-binary compounds were also determined. - Abstract: The phase equilibria in the Mg–Zn–Ag ternary system at 300 °C were investigated using three diffusion couples and 35 key samples. Scanning electron microscopy (SEM) equipped with energy-dispersive spectroscope (EDS) and X-ray diffraction (XRD) techniques were used for homogeneity ranges and crystal structure determination. Large solid solubility limits, due to substitution among Mg, Zn and Ag atoms in Mg{sub 3}Ag and MgZn{sub 2} phases, were observed in the present work. Solid solubility limits of Ag and Zn in the hcp (Mg) phase were found to be less than 1 at.%. The extended solid solubilities of the Mg{sub 12}Zn{sub 13}, Mg{sub 2}Zn{sub 3}, MgZn{sub 2} (C14), Mg{sub 2}Zn{sub 11}, Ag{sub 5}Zn{sub 8} and hcp (AgZn{sub 3}) sub-binary compounds were also determined in the Mg–Zn–Ag ternary system. In addition, a bcc continuous ternary solid solution forms between MgAg (bcc-B2) and AgZn (bcc-A2) at 300 °C.

[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.

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.)

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

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

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…

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 ...

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.

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)

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.

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...

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.

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.)

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.

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.

Monosilicide-disilicide-silicon phase equilibria in the nickel-platinum-silicon and nickel-palladium-silicon systems

Science.gov (United States)

Loomans, M. E.; Chi, D. Z.; Chua, S. J.

2004-10-01

Bulk-phase equilibria in Ni-rich/Si-rich alloys of the Ni-Pt-Si and Ni-Pd-Si systems were investigated. Results suggest that a bulk monosilicide solid solution, containing up to at least 11 at. pct Pt, exists in the Ni-Pt-Si system. Monosilicides containing more than 11 at. pct Pt were not examined. Results from both ternary systems point convincingly to the existence of a NiSi+Si↔NiSi2 eutectoid reaction near 700 °C in the Ni-Si binary system; data from the Ni-Pt-Si system, which yield the more accurate determination of the eutectoid temperature, place it at roughly 710 °C. The Pt and Pd concentrations of monosilicide in equilibrium with disilicide and Si were measured using energy-dispersive spectrometry (EDS) and were found to increase with temperature.

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).

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

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.

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

Mechanisms of Complete Turbulence Suppression in Turbidity Currents Driven by Mono-Disperse and Bi-Disperse Suspensions of Sediment

Directory of Open Access Journals (Sweden)

Mrugesh S. Shringarpure

2014-09-01

appears to have a logarithmic dependence on Reτ (Cantero et al. 2012. DNS of turbidity currents driven by bi-disperse suspension of sediments is also carried out and compared with the results of mono-disperse suspensions.

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

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

Metal-ion binding properties of (S)-1-[3-hydroxy-2-(phosphonomethoxy)propyl]cytosine (HPMPC, Cidofovir). A nucleotide analogue with activity against DNA viruses

Czech Academy of Sciences Publication Activity Database

Blindauer, C. A.; Sigel, A.; Operschall, B. P.; Holý, Antonín; Sigel, H.

2018-01-01

Roč. 472, Mar 1 (2018), s. 283-294 ISSN 0020-1693 Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * antivirals * chelates * isomeric equilibria * metal ion complexes * nucleotide analogues Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 2.002, year: 2016

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

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....

Relation of wave energy and momentum with the plasma dispersion relation in an inhomogeneous plasma

International Nuclear Information System (INIS)

Berk, H.L.; Pfirsch, D.

1988-01-01

The expressions for wave energy and angular momentum commonly used in homogeneous and near-homogeneous media is generalized to inhomogeneous media governed by a nonlocal conductivity tensor. The expression for wave energy applies to linear excitations in an arbitrary three-dimensional equilibrium, while the expression for angular momentum applies to linear excitations of azimuthally symmetric equilibria. The wave energy E-script/sub wave/ is interpreted as the energy transferred from linear external sources to the plasma if there is no dissipation. With dissipation, such a simple interpretation is lacking as energy is also thermally absorbed. However, for azimuthally symmetric equilibria, the expression for the wave energy in a frame rotating with a frequency ω can be unambiguously separated from thermal energy. This expression is given by E-script/sub wave/ -ωL/sub wave/ l, where L/sub wave/ is the wave angular momentum defined in the text and l the azimuthal wavenumber and it is closely related to the real part of a dispersion relation for marginal stability. The imaginary part of the dispersion is closely related to the energy input into a system. Another useful quantity discussed is the impedance form, which can be used for three-dimensional equilibrium without an ignorable coordinate and the expression is closely related to the wave impedance used in antenna theory. Applications to stability theory are also discussed

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.

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.

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....

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.)

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)

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.

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.

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

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.

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.

Intramolecular stacking interactions in ternary copper(II) complexes formed by a heteroaromatic amine and 9-[2-(2-phosphonoethoxy)ethyl]adenine, a relative of the antiviral nucleotide analogue 9-[2-(phosphonomethoxy)ethyl]adenine

Czech Academy of Sciences Publication Activity Database

Fernández-Botello, A.; Holý, Antonín; Moreno, V.; Sigel, H.

2004-01-01

Roč. 98, - (2004), s. 2114-2124 ISSN 0162-0134 R&D Projects: GA MŠk OC D20.002 Institutional research plan: CEZ:AV0Z4055905 Keywords : adenine nucleotide analogues * intramolecular equilibria * isomeric complexes Subject RIV: CC - Organic Chemistry Impact factor: 2.225, year: 2004

Hyper-resistivity and electron thermal conductivity due to destroyed magnetic surfaces in axisymmetric plasma equilibria

Energy Technology Data Exchange (ETDEWEB)

Weening, R. H. [Department of Radiologic Sciences, Thomas Jefferson University, 901 Walnut Street, Philadelphia, Pennsylvania 19107-5233 (United States)

2012-06-15

In order to model the effects of small-scale current-driven magnetic fluctuations in a mean-field theoretical description of a large-scale plasma magnetic field B(x,t), a space and time dependent hyper-resistivity {Lambda}(x,t) can be incorporated into the Ohm's law for the parallel electric field E Dot-Operator B. Using Boozer coordinates, a theoretical method is presented that allows for a determination of the hyper-resistivity {Lambda}({psi}) functional dependence on the toroidal magnetic flux {psi} for arbitrary experimental steady-state Grad-Shafranov axisymmetric plasma equilibria, if values are given for the parallel plasma resistivity {eta}({psi}) and the local distribution of any auxiliary plasma current. Heat transport in regions of plasma magnetic surfaces destroyed by resistive tearing modes can then be modeled by an electron thermal conductivity k{sub e}({psi})=({epsilon}{sub 0}{sup 2}m{sub e}/e{sup 2}){Lambda}({psi}), where e and m{sub e} are the electron charge and mass, respectively, while {epsilon}{sub 0} is the permittivity of free space. An important result obtained for axisymmetric plasma equilibria is that the {psi}{psi}-component of the metric tensor of Boozer coordinates is given by the relation g{sup {psi}{psi}}({psi}){identical_to}{nabla}{psi} Dot-Operator {nabla}{psi}=[{mu}{sub 0}G({psi})][{mu}{sub 0}I({psi})]/{iota}({psi}), with {mu}{sub 0} the permeability of free space, G({psi}) the poloidal current outside a magnetic surface, I({psi}) the toroidal current inside a magnetic surface, and {iota}({psi}) the rotational transform.

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...

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.

Model for ICRF fast wave current drive in self-consistent MHD equilibria

International Nuclear Information System (INIS)

Bonoli, P.T.; Englade, R.C.; Porkolab, M.; Fenstermacher, M.E.

1993-01-01

Recently, a model for fast wave current drive in the ion cyclotron radio frequency (ICRF) range was incorporated into the current drive and MHD equilibrium code ACCOME. The ACCOME model combines a free boundary solution of the Grad Shafranov equation with the calculation of driven currents due to neutral beam injection, lower hybrid (LH) waves, bootstrap effects, and ICRF fast waves. The equilibrium and current drive packages iterate between each other to obtain an MHD equilibrium which is consistent with the profiles of driven current density. The ICRF current drive package combines a toroidal full-wave code (FISIC) with a parameterization of the current drive efficiency obtained from an adjoint solution of the Fokker Planck equation. The electron absorption calculation in the full-wave code properly accounts for the combined effects of electron Landau damping (ELD) and transit time magnetic pumping (TTMP), assuming a Maxwellian (or bi-Maxwellian) electron distribution function. Furthermore, the current drive efficiency includes the effects of particle trapping, momentum conserving corrections to the background Fokker Planck collision operator, and toroidally induced variations in the parallel wavenumbers of the injected ICRF waves. This model has been used to carry out detailed studies of advanced physics scenarios in the proposed Tokamak Physics Experiment (TPX). Results are shown, for example, which demonstrate the possibility of achieving stable equilibria at high beta and high bootstrap current fraction in TPX. Model results are also shown for the proposed ITER device

Dynamic actuation of glassy polymersomes through isomerization of a single azobenzene unit at the block copolymer interface

Science.gov (United States)

Molla, Mijanur Rahaman; Rangadurai, Poornima; Antony, Lucas; Swaminathan, Subramani; de Pablo, Juan J.; Thayumanavan, S.

2018-06-01

Nature has engineered exquisitely responsive systems where molecular-scale information is transferred across an interface and propagated over long length scales. Such systems rely on multiple interacting, signalling and adaptable molecular and supramolecular networks that are built on dynamic, non-equilibrium structures. Comparable synthetic systems are still in their infancy. Here, we demonstrate that the light-induced actuation of a molecularly thin interfacial layer, assembled from a hydrophilic- azobenzene -hydrophobic diblock copolymer, can result in a reversible, long-lived perturbation of a robust glassy membrane across a range of over 500 chemical bonds. We show that the out-of-equilibrium actuation is caused by the photochemical trans-cis isomerization of the azo group, a single chemical functionality, in the middle of the interfacial layer. The principles proposed here are implemented in water-dispersed nanocapsules, and have implications for on-demand release of embedded cargo molecules.

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)

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.

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.

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.

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)

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

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.

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.

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.

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.

Intramolecular .pi.-.pi. stacking interactions in aqueous solution in mixed-ligand copper (II) complexes formed by heteroaromatic amines and the nucleotide analogue (PME2AP), an isomer of the antivirally active (PMEA)

Czech Academy of Sciences Publication Activity Database

Fernández-Botello, A.; Holý, Antonín; Moreno, V.; Operschall, B. P.; Sigel, H.

2009-01-01

Roč. 362, č. 3 (2009), s. 799-810 ISSN 0020-1693 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : antiviral activity * intramolecular equilibria * isomeric complexes * phosphonate complexes Subject RIV: CC - Organic Chemistry Impact factor: 2.322, year: 2009

(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

Second-chance forward isomerization dynamics of the red/green cyanobacteriochrome NpR6012g4 from Nostoc punctiforme.

Science.gov (United States)

Kim, Peter W; Freer, Lucy H; Rockwell, Nathan C; Martin, Shelley S; Lagarias, J Clark; Larsen, Delmar S

2012-01-11

The primary ultrafast Z-to-E isomerization photodynamics of the phytochrome-related cyanobacteriochrome NpR6012g4 from Nostoc punctiforme was studied by transient absorption pump-dump-probe spectroscopy. A 2 ps dump pulse resonant with the stimulated emission band depleted 21% of the excited-state population, while the initial photoproduct Lumi-R was depleted by only 11%. We observed a red-shifted ground-state intermediate (GSI) that we assign to a metastable state that failed to isomerize fully. Multicomponent global analysis implicates the generation of additional Lumi-R from the GSI via crossing over the ground-state thermal barrier for full isomerization, explaining the discrepancy between excited-state and Lumi-R depletion by the dump pulse. This second-chance ground-state dynamics provides a plausible explanation for the unusually high quantum yield of 40% for the primary isomerization step in the forward reaction of NpR6012g4. © 2011 American Chemical Society

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.

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.

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.

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

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.

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.

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....

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.

Phase noise of dispersion-managed solitons

International Nuclear Information System (INIS)

Spiller, Elaine T.; Biondini, Gino

2009-01-01

We quantify noise-induced phase deviations of dispersion-managed solitons (DMS) in optical fiber communications and femtosecond lasers. We first develop a perturbation theory for the dispersion-managed nonlinear Schroedinger equation (DMNLSE) in order to compute the noise-induced mean and variance of the soliton parameters. We then use the analytical results to guide importance-sampled Monte Carlo simulations of the noise-driven DMNLSE. Comparison of these results with those from the original unaveraged governing equations confirms the validity of the DMNLSE as a model for many dispersion-managed systems and quantify the increased robustness of DMS with respect to noise-induced phase jitter.

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.

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...

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...

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

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.

Plume meander and dispersion in a stable boundary layer

Science.gov (United States)

Hiscox, April L.; Miller, David R.; Nappo, Carmen J.

2010-11-01

Continuous lidar measurements of elevated plume dispersion and corresponding micrometeorology data are analyzed to establish the relationship between plume behavior and nocturnal boundary layer dynamics. Contrasting nights of data from the JORNADA field campaign in the New Mexico desert are analyzed. The aerosol lidar measurements were used to separate the plume diffusion (plume spread) from plume meander (displacement). Mutiresolution decomposition was used to separate the turbulence scale (90 s). Durations of turbulent kinetic energy stationarity and the wind steadiness were used to characterize the local scale and submesoscale turbulence. Plume meander, driven by submesoscale wind motions, was responsible for most of the total horizontal plume dispersion in weak and variable winds and strong stability. This proportion was reduced in high winds (i.e., >4 m s-1), weakly stable conditions but remained the dominant dispersion mechanism. The remainder of the plume dispersion in all cases was accounted for by internal spread of the plume, which is a small eddy diffusion process driven by turbulence. Turbulence stationarity and the wind steadiness are demonstrated to be closely related to plume diffusion and plume meander, respectively.

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...

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.

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

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.

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.

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

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

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...

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.

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

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

Modeling phase equilibria of alkanols with the simplified PC-SAFT equation of state and generalized pure compound parameters

DEFF Research Database (Denmark)

Grenner, Andreas; Kontogeorgis, Georgios; von Solms, Nicolas

2007-01-01

The simplified PC-SAFT equation of state has been applied to liquid-liquid, vapor-liquid and solid-liquid equilibria for mixtures containing 1-or 2-alkanols with alkanes, aromatic hydrocarbons, CO2 and water. For the alkanols we use generalized pure compound parameters. This means that two...... of the physical pure compound parameters, in (segment number) and or (segment diameter), are obtained from linear extrapolations, since m and m sigma(3), increase linearly with respect to the molar mass, and moreover, the two association parameters (association energy and association volume) were assumed...... to be constant for all alkanols. Only the dispersion energy is fitted to experimental data. Thus it is possible to estimate parameters for several 1-and 2-alkanols. The final aim is to develop a group contribution approach for PC-SAFT which is suitable for complex compounds, considering that the motivation...

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)

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

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.

Modeling solid-fuel dispersal during slow loss-of-flow-type transients

International Nuclear Information System (INIS)

DiMelfi, R.J.; Fenske, G.R.

1981-01-01

The dispersal, under certain accident conditions, of solid particles of fast-reactor fuel is examined in this paper. In particular, we explore the possibility that solid-fuel fragmentation and dispersal can be driven by expanding fission gas, during a slow LOF-type accident. The consequences of fragmentation are studied in terms of the size and speed of dispersed particles, and the overall quantity of fuel moved. (orig.)

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....

Quantum optimal control pathways of ozone isomerization dynamics subject to competing dissociation: A two-state one-dimensional model

International Nuclear Information System (INIS)

Kurosaki, Yuzuru; Ho, Tak-San; Rabitz, Herschel

2014-01-01

We construct a two-state one-dimensional reaction-path model for ozone open → cyclic isomerization dynamics. The model is based on the intrinsic reaction coordinate connecting the cyclic and open isomers with the O 2 + O asymptote on the ground-state 1 A ′ potential energy surface obtained with the high-level ab initio method. Using this two-state model time-dependent wave packet optimal control simulations are carried out. Two possible pathways are identified along with their respective band-limited optimal control fields; for pathway 1 the wave packet initially associated with the open isomer is first pumped into a shallow well on the excited electronic state potential curve and then driven back to the ground electronic state to form the cyclic isomer, whereas for pathway 2 the corresponding wave packet is excited directly to the primary well of the excited state potential curve. The simulations reveal that the optimal field for pathway 1 produces a final yield of nearly 100% with substantially smaller intensity than that obtained in a previous study [Y. Kurosaki, M. Artamonov, T.-S. Ho, and H. Rabitz, J. Chem. Phys. 131, 044306 (2009)] using a single-state one-dimensional model. Pathway 2, due to its strong coupling to the dissociation channel, is less effective than pathway 1. The simulations also show that nonlinear field effects due to molecular polarizability and hyperpolarizability are small for pathway 1 but could become significant for pathway 2 because much higher field intensity is involved in the latter. The results suggest that a practical control may be feasible with the aid of a few lowly excited electronic states for ozone isomerization

Phase equilibria in the ternary In-Ni-Sn system at 700 °C.

Science.gov (United States)

Schmetterer, C; Zemanova, A; Flandorfer, H; Kroupa, A; Ipser, H

2013-04-01

The phase equilibria of the ternary system In-Ni-Sn were investigated experimentally at 700 °C using X-ray diffraction (XRD) and scanning electron microscopy (SEM) including electron micro probe analysis (EMPA) and energy dispersive X-ray spectroscopy (EDX). A corresponding isothermal section was established based on these results. This particular temperature was chosen because it allowed obtaining reliable results within reasonable time. The existence of the ternary phase InNi 6 Sn 5 was confirmed whereas the ternary compound In 2 NiSn, reported earlier in literature, was found to be part of a large solid solution field based on binary InNi. The ternary solubility of the binary phases was established, and continuous solid solutions were found between the isostructural phases Ni 3 Sn LT and InNi 3 as well as between Ni 3 Sn 2 HT and InNi 2 . In addition, this isothermal section could be well reproduced by CALPHAD modelling. The resulting calculated isotherm at 700 °C is presented, too, and compared with the experimental results.

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.

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.

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

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

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

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).

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

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)

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.

A radioisotope study of the dispersion of ferric hydroxide floc in Bass Strait

International Nuclear Information System (INIS)

Davison, A.

1983-01-01

The dispersion of ferric hydroxide floc in Bass Strait waters adjacent to Burnie, Tasmania, has been investigated using radioisotope tracer techniques. Gold-198 labelled floc was employed to follow the movement of floc produced by dilution of the iron-rich effluent from a titanium dioxide plant. Dispersion was determined under calm and storm conditions. Tidal and wind-driven currents were measured, oscillating wave generated currents were calculated, and lateral and vertical dispersion coefficients were determined. It is concluded that floc disperses episodically during storms. The agglomerated floc remains trapped in a stable seabed layer which spreads slowly at seabed level when wind velocities are less than 15 m s -1 . When wind velocities exceed this level, the wave generated oscillating currents at seabed level, 30 m below the surface, are strong enough to raise the floc into suspension where advective dispersion occurs. Since tidal currents in the area are negligible, the direction of floc movement depends on the direction of the wind-driven current during each storm

Curvature driven instabilities in toroidal plasmas

International Nuclear Information System (INIS)

Andersson, P.

1986-11-01

The electromagnetic ballooning mode, the curvature driven trapped electron mode and the toroidally induced ion temperature gradient mode have been studies. Eigenvalue equations have been derived and solved both numerically and analytically. For electromagnetic ballooning modes the effects of convective damping, finite Larmor radius, higher order curvature terms, and temperature gradients have been investigated. A fully toroidal fluid ion model has been developed. It is shown that a necessary and sufficient condition for an instability below the MHD limit is the presence of an ion temperature gradient. Analytical dispersion relations giving results in good agreement with numerical solutions are also presented. The curvature driven trapped electron modes are found to be unstable for virtually all parameters with growth rates of the order of the diamagnetic drift frequency. Studies have been made, using both a gyrokinetic ion description and the fully toroidal ion model. Both analytical and numerical results are presented and are found to be in good agreement. The toroidally induced ion temperature gradients modes are found to have a behavior similar to that of the curvature driven trapped electron modes and can in the electrostatic limit be described by a simple quadratic dispersion equation. (author)

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)

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)

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.

Axial dispersion via shear-enhanced diffusion in colloidal suspensions

KAUST Repository

Griffiths, I. M.

2012-03-01

The familiar example of Taylor dispersion of molecular solutes is extended to describe colloidal suspensions, where the fluctuations that contribute to dispersion arise from hydrodynamic interactions. The generic scheme is illustrated for a suspension of particles in a pressure-driven pipe flow, with a concentration-dependent diffusivity that captures both the shear-induced and Brownian contributions. The effect of the cross-stream migration via shear-induced diffusion is shown to dramatically reduce the axial dispersion predicted by classical Taylor dispersion for a molecular solute. Analytic and numerical solutions are presented that illustrate the effect of the concentration dependence of this nonlinear hydrodynamic mechanism. Copyright © EPLA, 2012.

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.

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.

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.

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.

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).

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...

Excitation function and isomeric ratio of Tc-isotopes from the 93Nb(α, xn) reaction

International Nuclear Information System (INIS)

Kim, K.; Kim, G.N.; Naik, H.; Zaman, M.; Yang, S.-C.; Song, T.-Y.; Guin, R.; Das, S.K.

2015-01-01

The excitation functions of 94–96 Tc isotopes and independent isomeric ratios of 93m, g Tc, 94m, g Tc, and 95m, g Tc from the 93 Nb(α, xn) reaction within the energy range below 40 MeV have been determined by using a stacked-foil activation and an off-line γ-ray spectrometric technique at the Variable Energy Cyclotron Center, Kolkota, India. The excitation function of 94–96 Tc in the 93 Nb(α, xn) reaction was also calculated by using the computer code TALYS 1.6. The present data are found to be in general agreement with the literature data but have similar trend with some deviation from calculated data of the TALYS 1.6 code. The isomeric ratios of 93m, g Tc, 94m, g Tc, and 95m, g Tc in the 93 Nb(α, xn) reactions from the present work and literature data were compared with similar data in the 93 Nb( 3 He, xn) and 96 Mo(p, xn) reactions. In all the three reactions, the isomeric ratios increase with the increasing excitation energy. However, at all excitation energies, the isomeric ratios of 93m, g Tc, 94m, g Tc, and 95m, g Tc in the 93 Nb(α, xn) and 93 Nb( 3 He, xn) reactions are higher than those in the 96 Mo(p, xn) reactions, which indicate the role of input angular momentum besides excitation energy. Above the excitation energy of 35–55 MeV, the isomeric ratios of 95m, g Tc, 94m, g Tc, and 93m, g Tc decrease in all the 93 Nb(α, xn), 93 Nb( 3 He, xn) and 96 Mo(p, xn) reactions. This decreasing trend at higher excitation energy indicates the starting of pre-equilibrium reaction, which depends on the target, projectile, and type of reaction products

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...

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.

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.

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 ...

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.

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.

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)

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.

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.

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.

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

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

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)

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

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

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.

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

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...

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

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.

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…

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

Statistical Physics of Colloidal Dispersions.

Science.gov (United States)

Canessa, E.

Available from UMI in association with The British Library. Requires signed TDF. This thesis is concerned with the equilibrium statistical mechanics of colloidal dispersions which represent useful model systems for the study of condensed matter physics; namely, charge stabilized colloidal dispersions and polymer stabilized colloidal dispersions. A one-component macroparticle approach is adopted in order to treat the macroscopic and microscopic properties of these systems in a simple and comprehensive manner. The thesis opens with the description of the nature of the colloidal state before reviewing some basic definitions and theory in Chapter II. In Chapter III a variational theory of phase equilibria based on the Gibbs-Bogolyobov inequality is applied to sterically stabilized colloidal dispersions. Hard spheres are chosen as the reference system for the disordered phases while an Einstein model is used for the ordered phases. The new choice of pair potential, taken for mathematical convenience, is a superposition of two Yukawa functions. By matching a double Yukawa potential to the van der Waals attractive potential at different temperatures and introducing a purely temperature dependent coefficient to the repulsive part, a rich variety of observed phase separation phenomena is qualitatively described. The behaviour of the potential is found to be consistent with a small decrease of the polymer layer thickness with increasing temperature. Using the same concept of a collapse transition the non-monotonic second virial coefficient is also explained and quantified. It is shown that a reduction of the effective macroparticle diameter with increasing temperature can only be partially examined from the point of view of a (binary-) polymer solution theory. This chapter concludes with the description of the observed, reversible, depletion flocculation behaviour. This is accomplished by using the variational formalism and by invoking the double Yukawa potential to allow

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

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.)

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

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.

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

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

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

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.

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

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

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

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.

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

Development of PRIME for irradiation performance analysis of U-Mo/Al dispersion fuel

Science.gov (United States)

Jeong, Gwan Yoon; Kim, Yeon Soo; Jeong, Yong Jin; Park, Jong Man; Sohn, Dong-Seong

2018-04-01

A prediction code for the thermo-mechanical performance of research reactor fuel (PRIME) has been developed with the implementation of developed models to analyze the irradiation behavior of U-Mo dispersion fuel. The code is capable of predicting the two-dimensional thermal and mechanical performance of U-Mo dispersion fuel during irradiation. A finite element method was employed to solve the governing equations for thermal and mechanical equilibria. Temperature- and burnup-dependent material properties of the fuel meat constituents and cladding were used. The numerical solution schemes in PRIME were verified by benchmarking solutions obtained using a commercial finite element analysis program (ABAQUS). The code was validated using irradiation data from RERTR, HAMP-1, and E-FUTURE tests. The measured irradiation data used in the validation were IL thickness, volume fractions of fuel meat constituents for the thermal analysis, and profiles of the plate thickness changes and fuel meat swelling for the mechanical analysis. The prediction results were in good agreement with the measurement data for both thermal and mechanical analyses, confirming the validity of the code.

Isomerization of Internal Alkynes to Iridium(III Allene Complexes via C–H Bond Activation: Expanded Substrate Scope, and Progress towards a Catalytic Methodology

Directory of Open Access Journals (Sweden)

Neha Phadke

2015-11-01

Full Text Available The synthesis of a series of allene complexes (POCOPIr(η2-RC=.=CR’ 1b–4b (POCOP = 2,6-bis(di-tert-butylphosphonitobenzene via isomerization of internal alkynes is reported. We have demonstrated that the application of this methodology is viable for the isomerization of a wide variety of alkyne substrates. Deuterium labeling experiments support our proposed mechanism. The structures of the allene complexes 1b–4b were determined using spectroscopic data analysis. Additionally, the solid-state molecular structure of complex 2b was determined using single crystal X-ray diffraction studies and it confirmed the assignment of an iridium-bound allene isomerization product. The rates of isomerization were measured using NMR techniques over a range of temperatures to allow determination of thermodynamic parameters. Finally, we report a preliminary step towards developing a catalytic methodology; the allene may be liberated from the metal center by exposure of the complex to an atmosphere of carbon monoxide.

Measurement and modeling of high-pressure (vapour + liquid) equilibria of (CO{sub 2} + alcohol) binary systems

Energy Technology Data Exchange (ETDEWEB)

Gutierrez, Jorge E.; Bejarano, Arturo [Departamento de Ingenieria Quimica y Ambiental, Universidad Tecnica Federico Santa Maria, Avda. Espana 1680, Valparaiso (Chile); Fuente, Juan C. de la, E-mail: juan.delafuente@usm.c [Departamento de Ingenieria Quimica y Ambiental, Universidad Tecnica Federico Santa Maria, Avda. Espana 1680, Valparaiso (Chile); Centro Regional de Estudios en Alimentos Saludables, Blanco 1623, Valparaiso (Chile)

2010-05-15

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 <5%. Complementary isothermal (vapour + liquid) equilibria results are reported for the (CO{sub 2} + 1-propanol), (CO{sub 2} + 2-methyl-1-propanol), (CO{sub 2} + 3-methyl-1-butanol), and (CO{sub 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{sub 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.

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.

Confinement margins for ignition and driven operation in Iter Eda ID

International Nuclear Information System (INIS)

Johner, J.

1995-09-01

Preliminary calculations for ITER EDA ID have been performed using the 1/2D thermal equilibrium code HELIOS. It is found that: - The maximum ignition margin for ITER ID (29%) is 6% less than for ITER OD (35%) and 5% less than for ITER CDA (34%). - Decreasing the ration τ * He /τ E from the nominal value 10 to a value of 5 gives a 12% gain in the maximum ignition margin. Increasing the ration from 10 to 15 causes a 22% loss in the margin. Furthermore, ignited equilibria non longer exist for τ * He /τ E ≥ 17.6. - Operation in driven mode with 50 MW of external power increases the confinement capability by 13%. With 100 MW, the improvement is 24%. - Lowering the fusion power from 1500 to 1000 MW slightly improves the maximum ignition margin (+5%) and allows operation below the Greenwald density limit. - A 10% reduction of the toroidal magnetic field with a correlative diminution of the plasma current for constant safety factor operation, causes a dramatic reduction (-18%) of the maximum ignition margin. - A fraction of neon of 0.68% would completely suppress the ignition margin. Furthermore, ignited equilibria, with the nominal fusion power and τ * He /τ E , no longer exist when the neon fraction exceeds 0.75%. (Author). 2 refs., 10 figs

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

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

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

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

Surface currents on the plasma-vacuum interface in MHD equilibria

Science.gov (United States)

Hanson, James

2017-10-01

The VMEC non-axisymmetric MHD equilibrium code can compute free-boundary equilibria. Since VMEC assumes that magnetic fields within the plasma form closed and nested flux surfaces, the plasma-vacuum interface is a flux surface, and the total magnetic field there has no normal component. VMEC imposes this condition of zero normal field using the potential formulation of Merkel, and solves a Neumann problem for the magnetic potential in the exterior region. This boundary condition necessarily admits the possibility of a surface current on the interface. While this surface current may be small in MHD equilibrium, it is readily computed in terms of the magnetic potentials in both the interior and exterior regions, evaluated on the surface. If only the external magnetic potential is known (as in VMEC), then the surface current can be computed from the discontinuity of the tangential field across the interface. Examples of the surface current for VMEC equilibria will be shown for a zero-pressure stellarator equilibrium. Field-line following of the vacuum magnetic field shows magnetic islands within the plasma region.

Application of cinchona-sulfonate-based chiral zwitterionic ion exchangers for the separation of proline-containing dipeptide rotamers and determination of on-column isomerization parameters from dynamic elution profiles.

Science.gov (United States)

Wernisch, Stefanie; Trapp, Oliver; Lindner, Wolfgang

2013-09-17

The interconversion of cis and trans isomers of dipeptides containing C-terminal proline was studied by dynamic chromatography on zwitterionic chiral stationary phases at temperatures ranging from -15°C to +45°C The cis-trans isomers could be separated below 0°C and above 0-10°C plateau formation and peak coalescence phenomena occurred, which is characteristic for a dynamic process at the time-scale of partitioning. At and above room temperature, full coalescence was observed, which allowed separations of enantiomers without interference from interconversion effects. Analysis of the dynamic elution profiles of the interconverting peptides allowed the determination of isomerization rate constants and thermodynamic activation parameters (isomerization enthalpy, entropy and activation energy). In accordance with established results, isomerization rates and thermodynamic parameters were found to depend on the nature of the N-terminal amino acid. Isomerization barriers were only slightly lower than values determined with other methods but significant differences in the relative contributions of the activation enthalpy and entropy as well as isomerization rates pointed toward selector-moderated isomerization dynamics. Copyright © 2013 Elsevier B.V. All rights reserved.

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...

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.

Dispersal Kernel Determines Symmetry of Spread and Geographical Range for an Insect

International Nuclear Information System (INIS)

Holland, J.D.

2009-01-01

The distance from a source patch that dispersing insects reach depends on the number of dispersers, or random draws from a probability density function called a dispersal kernel, and the shape of that kernel. This can cause asymmetrical dispersal between habitat patches that produce different numbers of dispersers. Spatial distributions based on these dynamics can explain several ecological patterns including mega populations and geographic range boundaries. I hypothesized that a locally extirpated long horned beetle, the sugar maple borer, has a new geographical range shaped primarily by probabilistic dispersal distances. I used data on occurrence from Ontario, Canada to construct a model of geographical range in Indiana, USA based on maximum dispersal distance scaled by habitat area. This model predicted the new range boundary within 500 m very accurately. This beetle may be an ideal organism for exploring spatial dynamics driven by dispersal.

The Dispersion of Employees' Wage Increases and Firm Performance

DEFF Research Database (Denmark)

Grund, Christian; Westergård-Nielsen, Niels Chr.

does not induce any monetary incentives. Evidence from unique Danish linked employer employee data shows that large dispersion of wage growth within firms is generally connected with low firm performance. The results are mainly driven by white collar rather than blue collar workers.......In this contribution, we examine the interrelation between intra-firm wage increases and firm performance. Previous studies have focused on the dispersion of wages in order to examine for the empirical dominance of positive monetary incentives effects compared to adverse effects due to fairness...... considerations. We argue that the dispersion of wage increases rather than wage levels is a crucial measure for monetary incentives in firms. The larger the dispersion of wage increases the higher the amount of monetary incentives in firms. In contrast, huge wage inequality without any promotion possibilities...

Food supplementation mitigates dispersal-dependent differences in nest defence in a passerine bird.

Science.gov (United States)

Récapet, Charlotte; Daniel, Grégory; Taroni, Joëlle; Bize, Pierre; Doligez, Blandine

2016-05-01

Dispersing and non-dispersing individuals often differ in phenotypic traits (e.g. physiology, behaviour), but to what extent these differences are fixed or driven by external conditions remains elusive. We experimentally tested whether differences in nest-defence behaviour between dispersing and non-dispersing individuals changed with local habitat quality in collared flycatchers, by providing additional food during the nestling rearing period. In control (non-food-supplemented) nests, dispersers were less prone to defend their brood compared with non-dispersers, whereas in food-supplemented nests, dispersing and non-dispersing individuals showed equally strong nest defence. We discuss the importance of dispersal costs versus adaptive flexibility in reproductive investment in shaping these differences in nest-defence behaviour between dispersing and non-dispersing individuals. Irrespective of the underlying mechanisms, our study emphasizes the importance of accounting for environmental effects when comparing traits between dispersing and non-dispersing individuals, and in turn assessing the costs and benefits of dispersal. © 2016 The Author(s).

Transitional dispersive scenarios driven by mesoscale flows on complex terrain under strong dry convective conditions

Directory of Open Access Journals (Sweden)

J. L. Palau

2009-01-01

Full Text Available By experimentation and modelling, this paper analyses the atmospheric dispersion of the SO₂ emissions from a power plant on complex terrain under strong convective conditions, describing the main dispersion features as an ensemble of "stationary dispersive scenarios" and reformulating some "classical" dispersive concepts to deal with the systematically monitored summer dispersive scenarios in inland Spain. The results and discussions presented arise from a statistically representative study of the physical processes associated with the multimodal distribution of pollutants aloft and around a 343-m-tall chimney under strong dry convective conditions in the Iberian Peninsula. This paper analyses the importance of the identification and physical implications of transitional periods for air quality applications. The indetermination of a transversal plume to the preferred transport direction during these transitional periods implies a small (or null physical significance of the classical definition of horizontal standard deviation of the concentration distribution.

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.

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.

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.

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...

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.

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.

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....

Tsunami-driven rafting: Transoceanic species dispersal and implications for marine biogeography.

Science.gov (United States)

Carlton, James T; Chapman, John W; Geller, Jonathan B; Miller, Jessica A; Carlton, Deborah A; McCuller, Megan I; Treneman, Nancy C; Steves, Brian P; Ruiz, Gregory M

2017-09-29

The 2011 East Japan earthquake generated a massive tsunami that launched an extraordinary transoceanic biological rafting event with no known historical precedent. We document 289 living Japanese coastal marine species from 16 phyla transported over 6 years on objects that traveled thousands of kilometers across the Pacific Ocean to the shores of North America and Hawai'i. Most of this dispersal occurred on nonbiodegradable objects, resulting in the longest documented transoceanic survival and dispersal of coastal species by rafting. Expanding shoreline infrastructure has increased global sources of plastic materials available for biotic colonization and also interacts with climate change-induced storms of increasing severity to eject debris into the oceans. In turn, increased ocean rafting may intensify species invasions. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Positional isomerism-driven two 3D pillar-layered metal-organic frameworks: Syntheses, topological structures and photoluminescence properties

Energy Technology Data Exchange (ETDEWEB)

Sun, Yayong; Zhao, Siwei; Ma, Haoran; Han, Yi; Liu, Kang; Wang, Lei, E-mail: inorchemwl@126.com

2016-06-15

Two novel three-dimensional (3D) pillar-layered metal-organic frameworks (MOFs), namely [Zn{sub 2}(μ{sub 2}-OH)(boaba)(1,4-bmimb)]{sub n} (1) and {[Zn_5K_2(μ_2-H_2O)_2(boaba)_4(1,2-bmimb)_2(H_2O)_2]·H_2O}{sub n} (2), were prepared by hydrothermal reactions (H{sub 3}boaba=3,5-bis-oxyacetate-benzoic acid; 1,4-bmimb=1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene; 1,2-bmimb =1,2-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene). Notably, 1 exhibits a (3,5)-connected binodal (6{sup 3})(6{sup 9}·8)-gra net with binuclear [Zn{sub 2}(μ{sub 2}-OH)(COO)]{sup 2+} clusters, while 2 shows a novel (4,4,5,9)-connected 4-nodal net constructed from the unique Zn(II)-K(I) heterometal rod-like substructures. The results indicate that the disposition of the 2-methylimidazolyl groups of bis(imidazole) ligands have a significant effect on structural diversity. Moreover, the photoluminescence properties of 1 and 2 have been investigated. - Graphical abstract: Two novel 3D pillar-layered metal-organic coordination networks with aromatic multicarboxylate anion and bis(imidazole) ligands have been synthesized and structurally characterized. Display Omitted - Highlights: • It is rarely reported that metal-organic frameworks prepared with 3,5-bis-oxyacetate-benzoic acid. • Two metal-organic frameworks based on positional isomeric ligands were synthesized and structurally characterized. • Compond 1 displays unique (3,5)-connected binodal gra topology. • Compound 2 exhibits (4,4,5,9)-connected 4-nodal topology based on the Zn(II)-K(I) heterometal rod-like substructures. • The photoluminescence properties of compound 1 and 2 have been investigated.

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

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 ...

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

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.

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…

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.

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

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...

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...

Solid-state phase equilibria in the Fe-Pt-Pr ternary system at 1173 K

International Nuclear Information System (INIS)

Ren Jing; Gu Zhengfei; Cheng Gang; Zhou Huaiying

2005-01-01

The solid-state phase equilibria in the Fe-Pt-Pr ternary system at 1173 K (Pr ≤ 70%) were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS) techniques. The 1173 K isothermal section consists of 13 single-phase regions, 22 two-phase regions and 10 three-phase regions. At 1173 K, we have observed that the maximum solid solubility of Pt in α-Fe is below 1.5 at.% and the solid solution region of Pt in γ-Fe is from 2 to 35 at.%; the maximum solid solubility of Fe in Pt is 18 at.%. The maximum solubility of Fe in PrPt 5 , PrPt 3 , PrPt 2 , Pr 3 Pt 4 , PrPt, Pr 3 Pt 2 and Pr 7 Pt 3 is below 1 at.%. The maximum solubility of Pr in α-(Fe, Pt), γ-(Fe, Pt), FePt, FePt 3 and (Pt, Fe) (the solid solution of Fe in Pt) is 6, 2, 4, 4.5 and 1.5 at.%, respectively. In this work, it is found that the phase Pr 3 Pt 4 does not exist in the ternary system. The binary compounds Fe 7 Pr and Fe 2 Pr and any new ternary compounds were not observed

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 ...

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

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...

Advection and Taylor-Aris dispersion in rivulet flow

Science.gov (United States)

Al Mukahal, F. H. H.; Duffy, B. R.; Wilson, S. K.

2017-11-01

Motivated by the need for a better understanding of the transport of solutes in microfluidic flows with free surfaces, the advection and dispersion of a passive solute in steady unidirectional flow of a thin uniform rivulet on an inclined planar substrate driven by gravity and/or a uniform longitudinal surface shear stress are analysed. Firstly, we describe the short-time advection of both an initially semi-infinite and an initially finite slug of solute of uniform concentration. Secondly, we describe the long-time Taylor-Aris dispersion of an initially finite slug of solute. In particular, we obtain the general expression for the effective diffusivity for Taylor-Aris dispersion in such a rivulet, and discuss in detail its different interpretations in the special case of a rivulet on a vertical substrate.

Optically induced anisotropy in photo responsive sol-gel matrix bearing a silylated disperse red 1

International Nuclear Information System (INIS)

Choi, Dong Hoon; Cho, Kang Jin; Cha, Young Kwan; Oh, Sang Joon

2000-01-01

We synthesized the simple triethoxysilanes (SGDR1) bearing a disperse red 1 for thin film fabrication. The thin films were prepared using the solution of SGDR1 after hydrolysis and condensation. The films were annealed at two different temperatures such as 150.deg.C and 200.deg.C. Trans-to-cis photoisomerization was observed under the exposure of 532 nm light with UV-Vis absorption spectroscopy. The kinetic study of photoisomerization was performed in the film. Reorientation of the polar azobenzene molecules induced optical anisotropy under a linearly polarized light at 532 nm. The effect of aggregation of the chromophores and annealing of the silicon oxide in the matrix were studied on the dynamic properties of isomerization and induced birefringence

Influence of the temperature on the (liquid + liquid) phase equilibria of (water + 1-propanl + linalool or geraniol)

International Nuclear Information System (INIS)

Wan, Li; Li, Hengde; Huang, Cheng; Feng, Yuqing; Chu, Guoqiang; Zheng, Yuying; Tan, Wei; Qin, Yanlin; Sun, Dalei; Fang, Yanxiong

2017-01-01

Highlights: • Ternary LLEs containing linalool and geraniol are presented. • Distribution ratios of 1-propanol in the mixtures are examined. • Influence of the temperature on the LLE is studied. • The LLE data were correlated using the NRTL and UNIQUAC models. - Abstract: Linalool and geraniol are the primary components of rose oil, palmarosa oil, and citronella oil and many other essential oils, and two important compounds used in the flavour and fragrance, cosmetic or pharmaceutical industries. Phase equilibria (LLE, VLE, solubility, etc.) and related thermodynamic properties of a mixture are essential in the processes design and control of mass transfer process. In this work, experimental (liquid + liquid) equilibria data of the systems (water + 1-propanl + linalool) and (water + 1-propanl + geraniol) are presented. The (liquid + liquid) equilibria of both systems were determined with a tie-line method at T = (283.15, 298.15 and 313.15) K under atmospheric pressure. The well-known Hand, Bachman and Othmer–Tobias equations were used to test the reliability of the experimental values. The influence of the temperature on the (liquid + liquid) phase equilibria of the mixtures, the binodal curves and distribution ratios of 1-propanl are shown and discussed. Moreover, the NRTL and UNIQUAC models were applied to fit the data for both ternary systems. The interaction parameters obtained from both models successfully correlated the equilibrium compositions. Furthermore, the ternary systems could be represented using the binary parameters of the thermodynamic model with a function of temperature.

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.

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...

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.

Binary liquid-liquid equilibria of aniline-paraffin and furfural-paraffin systems

Energy Technology Data Exchange (ETDEWEB)

Sen, S.C.; Maity, S.; Ganguli, K.; Ray, P. (Calcutta Univ., (India))

1991-12-01

Liquid-liquid-equilibria (L-L-E) of hydrocarbon containing systems are of considerable commercial importance to refineries. But prediction of L-L-E of such systems is extremely difficult owing to the complex nature of the petroleum fluids. For treating such complex mixtures, a continuous component method is appropriate and for representing such liquids, a group contribution model like the UNIFAC is extremely convenient. It is, however, necessary to determine the appropriate group interaction parameters, and also to test the applicability of the UNIFAC method to these cases. Binary liquid-liquid-equilibria data for several aniline-paraffin and furfural-paraffin systems have been taken. These data along with data for other aniline-hydrocarbon and furfural-hydrocarbon systems from literature have been correlated using the UNIFAC model. The UNIFAC group interaction parameters have been found to have a linear temperature dependence. The CH{sub 2} groups in cyclo and non-cyclo paraffins require different interaction parameters. It was also found that a scaling of the combinatorial term is necessary for higher molecular weight hydrocarbons. 13 refs., 12 figs., 5 tabs.

Experimental vapor-liquid equilibria data for binary mixtures of xylene isomers

Directory of Open Access Journals (Sweden)

W.L. Rodrigues

2005-09-01

Full Text Available Separation of aromatic C8 compounds by distillation is a difficult task due to the low relative volatilities of the compounds and to the high degree of purity required of the final commercial products. For rigorous simulation and optimization of this separation, the use of a model capable of describing vapor-liquid equilibria accurately is necessary. Nevertheless, experimental data are not available for all binaries at atmospheric pressure. Vapor-liquid equilibria data for binary mixtures were isobarically obtained with a modified Fischer cell at 100.65 kPa. The vapor and liquid phase compositions were analyzed with a gas chromatograph. The methodology was initially tested for cyclo-hexane+n-heptane data; results obtained are similar to other data in the literature. Data for xylene binary mixtures were then obtained, and after testing, were considered to be thermodynamically consistent. Experimental data were regressed with Aspen Plus® 10.1 and binary interaction parameters were reported for the most frequently used activity coefficient models and for the classic mixing rules of two cubic equations of state.

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.

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

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.

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

Ruthenium Hydride/Brønsted Acid-Catalyzed Tandem Isomerization/N-Acyliminium Cyclization Sequence for the Synthesis of Tetrahydro-β-carbolines

DEFF Research Database (Denmark)

Hansen, Casper Lykke; Clausen, Janie Regitse Waël; Ohm, Ragnhild Gaard

2013-01-01

This paper describes an efficient tandem sequence for the synthesis of 1,2,3,4-tetrahydro-β-carbolines (THBCs) relying on a ruthenium hydride/Brønsted acid- catalyzed isomerization of allylic amides to N-acyliminium ion intermediates which are trapped by a tethered indolenucleophile. The methodol...... the Suzuki cross-coupling reaction to the isomerization/N-acyliminium cyclization sequence. Finally, diastereo- and enantioselective versions of the title reaction have been examined using substrate control (with dr >15: 1) and asymmetric catalysis (ee up to 57%), respectively...

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.

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.

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.

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

Measurement of excitation functions and analysis of isomeric population in some reactions induced by proton on natural indium at low energy

Science.gov (United States)

Muhammed Shan, P. T.; Musthafa, M. M.; Najmunnisa, T.; Mohamed Aslam, P.; Rajesh, K. K.; Hajara, K.; Surendran, P.; Nair, J. P.; Shanbagh, Anil; Ghugre, S.

2018-06-01

The excitation functions for reaction residues populated via 115In(p , p) 115 mIn, 115In(p , pn) 114 mIn, 115In(p , p 2 n) 113 mIn, 113In(p , p) 113 mIn, 115In(p , nα) 111 mCd, 115In(p , 3 n) 113Sn and 113In(p , n) 113Sn channels were measured over the proton energy range of 8-22 MeV using stacked foil activation technique. Theoretical analysis of the data were performed within the framework of two statistical model codes EMPIRE-3.2 and TALYS-1.8. Isomeric cross section ratio for isomeric pairs m,g 115In, m,g 114In, m,g 113In, 113Sn m,g and m,g 111Cd were determined for the first time. The dependence of isomeric cross section ratio on various factors are analysed.

Behavior of magnetic islands in 3D MHD equilibria of helical devices

International Nuclear Information System (INIS)

Hayashi, T.; Sato, T.; Nakajima, N.

1994-09-01

Magnetic island formation in three-dimensional finite-β equilibria in the H-1 Heliac is studied by using the HINT code. It is found that the size of a dangerous island should increase with β but that a destruction of the equilibrium at low β is avoided because the rotational transform evolves to exclude the rational surface concerned. At higher β there is evidence of near-resonant flux surface deformations which may lead to an equilibrium limit. A reconnected equilibrium at still higher β exhibits a double island structure which is similar to homoclinic phase portraits which have been observed after separatrix reconnection in Hamiltonian systems. Physical mechanism of the island formation in finite-β helical equilibria is investigated to confirm there are cases where the global effect of the Pfirsch-Schlueter currents is important. The earlier theory is extended to elucidate the occurence of the complete self-healing of island when the resistive interchange criterion satisfied. (author)

Experimental investigation of phase equilibria in the Zr-Cu-Ni ternary system

Energy Technology Data Exchange (ETDEWEB)

Yang, Mujin; Wang, Cuiping; Yang, Shuiyuan; Shi, Zhan; Han, Jiajia; Liu, Xingjun [Xiamen Univ. (China). College of Materials and Fujian Provincial Key Lab. of Materials Genome

2017-08-15

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{sub 7}Ni{sub 10}, ZrNi, ZrNi{sub 5}, Zr{sub 14}Cu{sub 51}, and Zr{sub 2}Cu{sub 9}, show a remarkable ternary solubility. A new ternary compound named τ{sub 3} (Zr{sub 31.1-30.7} . Cu{sub 28.5-40.3}Ni{sub 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.

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

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.)

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)

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.

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.

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.

(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

Development of PRIME for irradiation performance analysis of U-Mo/Al dispersion fuel

Energy Technology Data Exchange (ETDEWEB)

Jeong, Gwan Yoon; Kim, Yeon Soo; Jeong, Yong Jin; Park, Jong Man; Sohn, Dong-Seong

2018-04-01

A prediction code for the thermo-mechanical performance of research reactor fuel (PRIME) has been developed with the implementation of developed models to analyze the irradiation behavior of U-Mo dispersion fuel. The code is capable of predicting the two-dimensional thermal and mechanical performance of U-Mo dispersion fuel during irradiation. A finite element method was employed to solve the governing equations for thermal and mechanical equilibria. Temperature-and burnup-dependent material properties of the fuel meat constituents and cladding were used. The numerical solution schemes in PRIME were verified by benchmarking solutions obtained using a commercial finite element analysis program (ABAQUS).The code was validated using irradiation data from RERTR, HAMP-1, and E-FUTURE tests. The measured irradiation data used in the validation were IL thickness, volume fractions of fuel meat constituents for the thermal analysis, and profiles of the plate thickness changes and fuel meat swelling for the mechanical analysis. The prediction results were in good agreement with the measurement data for both thermal and mechanical analyses, confirming the validity of the code. (c) 2018 Elsevier B.V. All rights reserved.

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.

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

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.

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.

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.

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.

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.)

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.

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

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...

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.

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

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.

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

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

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.

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.

Isomerization of 2-butene-1,4-diol in aqueous solutions catalyzed by palladium(II) complexes

Energy Technology Data Exchange (ETDEWEB)

Kalabin, S.M.; Novikov, N.A.; Belov, A.P.

1989-02-01

The authors studied the isomerization of 2-butene-1,4-diol into 3-butene-1,2-diol at 18-25/degree/C. The concentrations of the diol and PdCl/sub 2/ were (1.0-5.0) /times/ 10/sup /minus/2/ mole/liter at 5-10-fold excess amounts of HCl and NaCl. These additives were used because of their inhibiting action on the oxidation of olefinic compounds. 3-Butene-1,2-diol was identified by /sup 1/H NMR method directly in the reaction solutions in which the reaction solutions in which the reactions in D/sub 2/O were carried out. It was found that palladium(II) complexes catalyze the isomerization of 2-butene-1,4-diol into 3-butene-1,2-diol. A mechanism is proposed for the reaction, which includes the intermediate formation of /eta//sup 3/-allyl complex of palladium with a coordinated hydroxyl group.

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.

First principles calculation of L21+A2 coherent equilibria in the Fe-Al-Ti system

International Nuclear Information System (INIS)

Alonso, Paula R.; Gargano, Pablo H.; Ramirez-Caballero, Gustavo E.; Balbuena, Perla B.; Rubiolo, Gerardo H.

2009-01-01

By combining first-principles density functional total energy calculations and statistical mechanics the ground state and the phase equilibria at finite temperatures of the ternary system Fe-Al-Ti have been investigated. Total energy calculations have been performed by means of the Wien 2k code to establish the ground state energetic. A cluster expansion method was therewith used to describe solid solutions. At several chosen finite temperatures the cluster variation method in the irregular tetrahedron approximation was employed in order to calculate the iron rich ternary bcc equilibria. It is confirmed that there are two kinds of phase separations of the bcc phase, A2+L2 1 and B2+L2 1 .

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.

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.

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

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...

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.

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.

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.

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

Measurement and modeling of high-pressure (vapor + liquid) equilibria of (CO{sub 2} + alkanol) binary systems

Energy Technology Data Exchange (ETDEWEB)

Bejarano, Arturo; Gutierrez, Jorge E. [Departamento de Ingenieria Quimica y Ambiental, Universidad Tecnica Federico Santa Maria, Avda. Espana 1680, Valparaiso (Chile); Araus, Karina A. [Departamento de Ingenieria Quimica y Bioprocesos, Pontificia Universidad Catolica de Chile, Avda. Vicuna Mackenna 4860, Macul, Santiago (Chile); Fuente, Juan C. de la, E-mail: juan.delafuente@usm.c [Departamento de Ingenieria Quimica y Ambiental, Universidad Tecnica Federico Santa Maria, Avda. Espana 1680, Valparaiso (Chile); Centro Regional de Estudios en Alimentos Saludables, Blanco 1623, Valparaiso (Chile)

2011-05-15

Research highlights: (Vapor + liquid) equilibria of three (CO{sub 2} + C{sub 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{sub 2} + 3-methyl-2-butanol), (CO{sub 2} + 2-pentanol), and (CO{sub 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{sub 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.

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

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)

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.

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.

Isobaric (vapor + liquid) equilibria of 1-ethyl-3-methylimidazolium ethylsulfate plus (propionaldehyde or valeraldehyde): Experimental data and prediction

International Nuclear Information System (INIS)

Alvarez, Victor H.; Mattedi, Silvana; Aznar, Martin

2011-01-01

Research highlights: → We report density, refraction index, and VLE for (propionaldehyde or valeraldehyde) + [emim][EtSO 4 ]. → The Peng -Robinson + Wong -Sandler + COSMO-SAC model was used to predict density and VLE. → The densities were predicted with deviations below than 2.3%. → The experimental VLE was predicted with deviations below than 1.6%. - Abstract: This paper reports the density, refraction index, and (vapor + liquid) equilibria (VLE) for binary systems {aldehyde + 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO 4 ])}: {propionaldehyde + [emim][EtSO 4 ]} and {valeraldehyde + [emim][EtSO 4 ]}. The uncertainties for the temperature, pressure, and compositions measurements for the phase equilibria are ±0.1 K, ±0.01 kPa and ±0.0004, respectively. A qualitative analysis of the variation of the properties with changes in solvent and temperature was performed. The Peng-Robinson equation of state (PR EoS), coupled with the Wong-Sandler mixing rule (WS), is used to describe the experimental data. To calculate activity coefficients we used three different models: NRTL, UNIQUAC, and COSMO-SAC. Since the predictive liquid activity coefficient model COSMO-SAC is used in the Wong-Sandler mixing rule, the resulting thermodynamic model is a completely predictive one. The prediction results for the density and for the (vapor + liquid) equilibria have a deviation lower than 2.3% and 1.6%, respectively. The (vapor + liquid) equilibria predictions show a good description for the propionaldehyde system and only a qualitative description for the valeraldehyde system.

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.

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

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...

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

Isomeric States in the Second and Third Well of the Potential and Long-Lived Superheavy Element

International Nuclear Information System (INIS)

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

1999-01-01

Recently, in a study of the 16 O + 197 Au and 28 Si + 181 Ta reactions near and below the Coulomb barrier, long-lived high spin isomeric states have been found by us in the second and third well of the potential-energy surfaces. Such isomeric states have very unusual physical properties. In addition to their very long lifetimes, much longer than of their corresponding ground states, they have very unusual decay properties. They may decay by 5 to 7 orders of magnitude enhanced alpha particles, in transitions from the second or third well of the potential in the parent nuclei to the respective well in the daughters, or by very retarded alpha particles, in transitions from the second well in the parent nucleus to normal states in the daughter, or from the third well in the parent to the second well in the daughter. They also may decay by long-lived proton activities, in transitions from the second well in the parent nucleus to the normal states in the daughter. Experimental evidences for all these new phenomena will be presented in the conference. The existence of long-lived isomeric states in the second and third well of the potential is very important when the production of superheavy elements is considered. Because of the very much reduced extra-push energy needed for their production, they may be produced much easier than the normal states, in reactions between very heavy nuclei. In particular, the discovery of the long-lived superheavy element with Z = 112 can consistently be understood

Nuclear isomerism in fission fragments produced by the spontaneous fission of {sup 252}Cf; Isomerisme nucleaire dans les fragments de fission produits dans la fission spontanee du {sup 252}Cf

Energy Technology Data Exchange (ETDEWEB)

Gautherin, C

1997-09-01

This thesis is devoted to the study of the nuclear structure of neutron-rich nuclei, via the search of isomeric nuclear states. Neutron-rich nuclei were produced in the spontaneous fission of {sup 252}Cf. The experimental study of isomeric states in these nuclei was performed with the {gamma}-array EUROGAM II, coupled to an additional and original fission fragment detector composed by photovoltaic cells, SAPhIR. The photovoltaic cells are well adapted to detect low energy heavy ions and have good energy and time resolutions to obtain a good fission fragment detection. This experiment led to the discovery of new isomeric states in {sup 135}Xe, {sup 104}Mo, {sup 146,147,148}Ce and {sup 152,154,156}Nd, with lifetimes between 60 ns and 2 {mu}s. Level schemes of these nuclei have been completed. An interpretation of the isomeric states in the nuclei {sup 154,156}Nd and {sup 156,158}Sm was performed by Hartree-Fock-Bogolyubov calculations using the DIS Gogny force with two quasi-particles excitations. The confrontation with the experimental results led to an interpretation of these isomeric states as K-isomers. (author)

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.

[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.

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

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)

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

Reactive dispersive contaminant transport in coastal aquifers: Numerical simulation of a reactive Henry problem

KAUST Repository

Nick, H.M.

2013-02-01

The reactive mixing between seawater and terrestrial water in coastal aquifers influences the water quality of submarine groundwater discharge. While these waters come into contact at the seawater groundwater interface by density driven flow, their chemical components dilute and react through dispersion. A larger interface and wider mixing zone may provide favorable conditions for the natural attenuation of contaminant plumes. It has been claimed that the extent of this mixing is controlled by both, porous media properties and flow conditions. In this study, the interplay between dispersion and reactive processes in coastal aquifers is investigated by means of numerical experiments. Particularly, the impact of dispersion coefficients, the velocity field induced by density driven flow and chemical component reactivities on reactive transport in such aquifers is studied. To do this, a hybrid finite-element finite-volume method and a reactive simulator are coupled, and model accuracy and applicability are assessed. A simple redox reaction is considered to describe the degradation of a contaminant which requires mixing of the contaminated groundwater and the seawater containing the terminal electron acceptor. The resulting degradation is observed for different scenarios considering different magnitudes of dispersion and chemical reactivity. Three reactive transport regimes are found: reaction controlled, reaction-dispersion controlled and dispersion controlled. Computational results suggest that the chemical components\\' reactivity as well as dispersion coefficients play a significant role on controlling reactive mixing zones and extent of contaminant removal in coastal aquifers. Further, our results confirm that the dilution index is a better alternative to the second central spatial moment of a plume to describe the mixing of reactive solutes in coastal aquifers. © 2012 Elsevier B.V.

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

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

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

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

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

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.)

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...

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.

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.

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.

Quantification of isomerically summed hydrocarbon contributions to crude oil by carbon number, double bond equivalent, and aromaticity using gas chromatography with tunable vacuum ultraviolet ionization.

Science.gov (United States)

Nowak, Jeremy A; Weber, Robert J; Goldstein, Allen H

2018-03-12

The ability to structurally characterize and isomerically quantify crude oil hydrocarbons relevant to refined fuels such as motor oil, diesel, and gasoline represents an extreme challenge for chromatographic and mass spectrometric techniques. This work incorporates two-dimensional gas chromatography coupled to a tunable vacuum ultraviolet soft photoionization source, the Chemical Dynamics Beamline 9.0.2 of the Advanced Light Source at the Lawrence Berkeley National Laboratory, with a time-of-flight mass spectrometer (GC × GC-VUV-TOF) to directly characterize and isomerically sum the contributions of aromatic and aliphatic species to hydrocarbon classes of four crude oils. When the VUV beam is tuned to 10.5 ± 0.2 eV, both aromatic and aliphatic crude oil hydrocarbons are ionized to reveal the complete chemical abundance of C 9 -C 30 hydrocarbons. When the VUV beam is tuned to 9.0 ± 0.2 eV only aromatic hydrocarbons are ionized, allowing separation of the aliphatic and aromatic fractions of the crude oil hydrocarbon chemical classes in an efficient manner while maintaining isomeric quantification. This technique provides an effective tool to determine the isomerically summed aromatic and aliphatic hydrocarbon compositions of crude oil, providing information that goes beyond typical GC × GC separations of the most dominant hydrocarbon isomers.

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

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...

Experimental investigation of phase equilibria in the Co-W-V ternary system

International Nuclear Information System (INIS)

Liu Xingjun; Zhu Yihong; Yu Yan; Wang Cuiping

2011-01-01

Highlights: → Three isothermal sections of the Co-W-V ternary system at 1100 deg. C, 1200 deg. C and 1300 deg. C were determined. → No ternary compound was found in the Co-W-V ternary system. → A stable liquid miscibility gap is newly discovered in the Co-W-V ternary system. → This work is of great essence to establish the thermodynamic database for the Co-based alloys. - Abstract: The phase equilibria in the Co-W-V ternary system were experimentally investigated by optical microscopy (OM), electron probe microanalysis (EPMA) and X-ray diffraction (XRD) on the equilibrated alloys. Three isothermal sections of the Co-W-V ternary system at 1100 deg. C, 1200 deg. C and 1300 deg. C were determined, and no ternary compound was found in this system. In addition, a novel phenomena induced by the liquid phase separation in the Co-W-V alloys was firstly discovered, suggesting that a stable liquid miscibility gap exists in the Co-W-V ternary system. The newly determined phase equilibria and firstly discovered phase separation phenomena in the Co-W-V system will provide important information for the development of Co-W based alloys.

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

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.

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.

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.

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.

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.

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.)

Computational fluid dynamics simulation of wind-driven inter-unit dispersion around multi-storey buildings: Upstream building effect

DEFF Research Database (Denmark)

Ai, Zhengtao; Mak, C.M.; Dai, Y.W.

2017-01-01

of such changed airflow patterns on inter-unit dispersion characteristics around a multi-storey building due to wind effect. Computational fluid dynamics (CFD) method in the framework of Reynolds-averaged Navier-stokes modelling was employed to predict the coupled outdoor and indoor airflow field, and the tracer...... gas technique was used to simulate the dispersion of infectious agents between units. Based on the predicted concentration field, a mass conservation based parameter, namely re-entry ratio, was used to evaluate quantitatively the inter-unit dispersion possibilities and thus assess risks along...

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.

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.

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.

Numerical simulation of atmospheric dispersion in the vicinity of the Rocky Flats plant

International Nuclear Information System (INIS)

Bossert, J.E.; Poulos, G.S.

1993-01-01

The Atmospheric Studies in Complex Terrain (ASCOT) program sponsored a field experiment in the winter of 1991 near Rocky Flats, Colorado. Both meteorological and tracer dispersion measurements were taken. These two data sets provided an opportunity to investigate the influence of terrain-generated, radiatively-driven flows on the dispersion of the tracer. In this study, we use the Regional Atmospheric Modeling System (RAMS) to simulate meteorological conditions and tracer dispersion on the case night of 4--5 February 1991. The simulations were developed to examine the influence of nocturnal drainage flow from various topography regimes on the dispersion of tracer from the Rocky Flats plant. The simulation described herein demonstrates the extent to which Rocky Mountain drainage winds influence the flow at the mountain/plain interface for a particular case night, and shows the potential importance of canyon drainage on dispersion from the Rocky Flats area

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.

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

Predator-prey-subsidy population dynamics on stepping-stone domains with dispersal delays.

Science.gov (United States)

Eide, Ragna M; Krause, Andrew L; Fadai, Nabil T; Van Gorder, Robert A

2018-08-14

We examine the role of the travel time of a predator along a spatial network on predator-prey population interactions, where the predator is able to partially or fully sustain itself on a resource subsidy. The impact of access to food resources on the stability and behaviour of the predator-prey-subsidy system is investigated, with a primary focus on how incorporating travel time changes the dynamics. The population interactions are modelled by a system of delay differential equations, where travel time is incorporated as discrete delay in the network diffusion term in order to model time taken to migrate between spatial regions. The model is motivated by the Arctic ecosystem, where the Arctic fox consumes both hunted lemming and scavenged seal carcass. The fox travels out on sea ice, in addition to quadrennially migrating over substantial distances. We model the spatial predator-prey-subsidy dynamics through a "stepping-stone" approach. We find that a temporal delay alone does not push species into extinction, but rather may stabilize or destabilize coexistence equilibria. We are able to show that delay can stabilize quasi-periodic or chaotic dynamics, and conclude that the incorporation of dispersal delay has a regularizing effect on dynamics, suggesting that dispersal delay can be proposed as a solution to the paradox of enrichment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Comparison of Separation of Seed Oil Triglycerides Containing Isomeric Conjugated Octadecatrienoic Acid Moieties by Reversed-Phase HPLC

Directory of Open Access Journals (Sweden)

Anh Van Nguyen

2017-12-01

Full Text Available 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, Centranthus ruber, Momordica charantia, Trichosanthes anguina, Punica granatum, Thladiantha dubia, Valeriana officinalis, and Vernicia montana. It was found that a sequence of elution of TGs of the same types is the same without any inversions for full range of mobile phase compositions: punicic (C18:39Z11E13Z < jacaric (C18:38Z10E12Z < catalpic (C18:39E11E13Z < α-eleostearic (C18:39Z11E13E < calendic (C18:38E10E12Z < β-eleostearic (C18:39E11E13E < all-E calendic (C18:38E10E12E acids. TGs and fatty acid compositions were calculated for all oil samples. Regularities of solute retentions as a function of isomeric conjugated octadecatrienoic acid moiety structure are discussed. Thus, it was proven that it is possible to differentiate TGs of complex composition with moieties of all natural CLnA by retention control accomplished by electronic spectra comparison, even though there are only three types of electronic-vibration spectra for seven isomeric CLnA.

Differential Selectivity of the Escherichia coli Cell Membrane Shifts the Equilibrium for the Enzyme-Catalyzed Isomerization of Galactose to Tagatose▿

Science.gov (United States)

Kim, Jin-Ha; Lim, Byung-Chul; Yeom, Soo-Jin; Kim, Yeong-Su; Kim, Hye-Jung; Lee, Jung-Kul; Lee, Sook-Hee; Kim, Seon-Won; Oh, Deok-Kun

2008-01-01

An Escherichia coli galactose kinase gene knockout (ΔgalK) strain, which contains the l-arabinose isomerase gene (araA) to isomerize d-galactose to d-tagatose, showed a high conversion yield of tagatose compared with the original galK strain because galactose was not metabolized by endogenous galactose kinase. In whole cells of the ΔgalK strain, the isomerase-catalyzed reaction exhibited an equilibrium shift toward tagatose, producing a tagatose fraction of 68% at 37°C, whereas the purified l-arabinose isomerase gave a tagatose equilibrium fraction of 36%. These equilibrium fractions are close to those predicted from the measured equilibrium constants of the isomerization reaction catalyzed in whole cells and by the purified enzyme. The equilibrium shift in these cells resulted from the higher uptake and lower release rates for galactose, which is a common sugar substrate, than for tagatose, which is a rare sugar product. A ΔmglB mutant had decreased uptake rates for galactose and tagatose, indicating that a methylgalactoside transport system, MglABC, is the primary contributing transporter for the sugars. In the present study, whole-cell conversion using differential selectivity of the cell membrane was proposed as a method for shifting the equilibrium in sugar isomerization reactions. PMID:18263746

Differential selectivity of the Escherichia coli cell membrane shifts the equilibrium for the enzyme-catalyzed isomerization of galactose to tagatose.

Science.gov (United States)

Kim, Jin-Ha; Lim, Byung-Chul; Yeom, Soo-Jin; Kim, Yeong-Su; Kim, Hye-Jung; Lee, Jung-Kul; Lee, Sook-Hee; Kim, Seon-Won; Oh, Deok-Kun

2008-04-01

An Escherichia coli galactose kinase gene knockout (DeltagalK) strain, which contains the l-arabinose isomerase gene (araA) to isomerize d-galactose to d-tagatose, showed a high conversion yield of tagatose compared with the original galK strain because galactose was not metabolized by endogenous galactose kinase. In whole cells of the DeltagalK strain, the isomerase-catalyzed reaction exhibited an equilibrium shift toward tagatose, producing a tagatose fraction of 68% at 37 degrees C, whereas the purified l-arabinose isomerase gave a tagatose equilibrium fraction of 36%. These equilibrium fractions are close to those predicted from the measured equilibrium constants of the isomerization reaction catalyzed in whole cells and by the purified enzyme. The equilibrium shift in these cells resulted from the higher uptake and lower release rates for galactose, which is a common sugar substrate, than for tagatose, which is a rare sugar product. A DeltamglB mutant had decreased uptake rates for galactose and tagatose, indicating that a methylgalactoside transport system, MglABC, is the primary contributing transporter for the sugars. In the present study, whole-cell conversion using differential selectivity of the cell membrane was proposed as a method for shifting the equilibrium in sugar isomerization reactions.

The evolution of conditional dispersal and reproductive isolation along environmental gradients.

Science.gov (United States)

Payne, Joshua L; Mazzucco, Rupert; Dieckmann, Ulf

2011-03-21

Dispersal modulates gene flow throughout a population's spatial range. Gene flow affects adaptation at local spatial scales, and consequently impacts the evolution of reproductive isolation. A recent theoretical investigation has demonstrated that local adaptation along an environmental gradient, facilitated by the evolution of limited dispersal, can lead to parapatric speciation even in the absence of assortative mating. This and other studies assumed unconditional dispersal, so individuals start dispersing without regard to local environmental conditions. However, many species disperse conditionally; their propensity to disperse is contingent upon environmental cues, such as the degree of local crowding or the availability of suitable mates. Here, we use an individual-based model in continuous space to investigate by numerical simulation the relationship between the evolution of threshold-based conditional dispersal and parapatric speciation driven by frequency-dependent competition along environmental gradients. We find that, as with unconditional dispersal, parapatric speciation occurs under a broad range of conditions when reproduction is asexual, and under a more restricted range of conditions when reproduction is sexual. In both the asexual and sexual cases, the evolution of conditional dispersal is strongly influenced by the slope of the environmental gradient: shallow environmental gradients result in low dispersal thresholds and high dispersal distances, while steep environmental gradients result in high dispersal thresholds and low dispersal distances. The latter, however, remain higher than under unconditional dispersal, thus undermining isolation by distance, and hindering speciation in sexual populations. Consequently, the speciation of sexual populations under conditional dispersal is triggered by a steeper gradient than under unconditional dispersal. Enhancing the disruptiveness of frequency-dependent selection, more box-shaped competition kernels

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

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.

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.